Topics1 12chem230

Topic 1: Gases
1. Temperature
2. Pressure (barometer, manometer)
3. Ideal Gas Laws PV = nRT
4. Density d =
nMW PM
V
=
RT
5. Effusion, Diffusion MW
1
6. vrms (Boltzman distribution) MW 3RT
7. Mixtures of gases P = X P = n RT P = P + P +...

1 1 tot
1
tot 1 2
V
8. Real Gases
Z vs. pressure graphs
van der Waals a and b
Topic 1: Gases 1
Atmosphere/Hurricanes
Acidification of the oceans
Pistons (combustion engine)
Balloons
Refrigeration
CO2 fire extinguishers
SCUBA diving
Air bags
Tire pressure
Ultrasound contrast agents
(microbubbles)
http://www.youtube.com/watch?v=8ZhvoHAL33A
What is a gas?
“The state of matter distinguished from the solid and liquid states by relatively
low density and viscosity, relatively great expansion and contraction with
changes in pressure and temperature, the ability to diffuse readily, and the
spontaneous tendency to become distributed uniformly throughout any
container.”
The American Heritage Dictionary of the English Language. The Free

Dictionary.”Gas.” Accessed August 27, 2010.
http://www.thefreedictionary.com/gas
http://www.youtube.com/watch?v=8ZhvoHAL33A
-in constant motion

-ideally no intermolecular interactions
-particles collide with walls of container and one another
1) Temperature: Average Kinetic Energy
∑ KE + KE
1 2 +KE3 +.....
n
If two bodies are at different temperatures, heat will flow from the warmer to
the cooler one until their temperatures are the same.
https://www.chem.wisc.edu/deptfiles/genchem/sstutorial/Text9/Tx92/tx92.html
Thermometer and
Temperature Scale
The temperature of an object is measured
indirectly by placing a calibrated device known
as a thermometer in contact with it. When
thermal equilibrium is obtained, the
temperature of the thermometer is the same
as the temperature of the object.
" 1K %
TKelvin = (TC C )$ o ' +273.15K
o
#1 C &
Coyne, Kristen. “Superconductivity: Current in a Cape and
" 5 o %
C Thermal Tights.” Magnet Lab. National High Magnetic Field
TC C = $ o '(TF o F − 32 oF )
o
Laboratory. Accessed August 27, 2010.
#9 F & http://www.magnet.fsu.edu/education/tutorials/magnetacad
emy/superconductivity101/fullarticle.html
2) Atmospheric Pressure (open system)
weight
force (F) mass * acceleration mass(m) * gravity(g)

Pressure (P) = = =
area (A) A A
Why do hammers have small heads?

Why do your ears pop on an airplane?
Atkins, Nolan, Updated 8/25/08

Lyndon State College Survey of Meteorology, Updated August 25,
2008http://apollo.lsc.vsc.edu/classes/met130/notes/chapter1/vert_dens2.html
How does a straw work?
vacuum
Measuring Pressure:
Mercury Barometer
When pressures are equal
mg
Patm = Pliquid =
A
Liquid Density
m
=d
V
m = d *V Vcylinder = hA
m = d * hA mg dhA * g
Pliquid = = = dhg
A A
CHEMICAL PRINCIPLES|ATKINS|JONES|LAVERMAN ©2013 W. H. FREEMAN AND COMPANY
Pressure Units vacuum
m
ma kg 2 kg
P= s
= 2 = 2 = 1Pa
A m ms 760 mm Hg
1 bar = 1.00 x 105 Pa = 100 kPa

1 atm
1 atm = 1.01 x105 Pa = 101 kPa
1 atm = 760 mm Hg* = 760 torr
*mm Hg is pressure exerted by a column of mercury at 15oC in a standard

gravitational field
1 atm = 14.7 lb/in2 (psi)

Manometers
U-shaped tube (usually)
that measures relative
pressure.
There is an equal pushing

point from both sides.
Pleft = Pright
Unknonw P = P0 + h Image from: efunda “Manometer
Pressure.” Hydrostatics: Manometer
Example. 2019,
https://www.efunda.com/formulae/fluid
s/manometer.cfm
3) P, V, n, R, T (closed system)
Gas molecules colliding with the sides of a
container
F(orce)
P(ressure) =
A(rea)
Glogster-Poster Yourself. “kinetic molecular theory.” Updated November 2009.

Accessed August 27, 2010.
http://erimui1.glogster.com/kinetic-molecular-theory/
What causes an€

increase in pressure?
Pressure (closed system)
Gas molecules colliding with the sides of a
container
F(orce)
P(ressure) =
A(rea)
Glogster-Poster Yourself. “kinetic molecular theory.” Updated November 2009.

Accessed August 27, 2010.
http://erimui1.glogster.com/kinetic-molecular-theory/
What causes an€

increase in pressure?
Smaller volume (V)

More moles of gas (n)
Faster moving gas particles (higher temperature) (T)
Boyles Law: Volume and Pressure (constant n, T)
Isotherms (constant temperature)
P*V = 25 at 300K
Lower, S. (2010) Retrieved September 6, 2016 from: http://www.chem1.com/acad/webtext/gas/gas_2.html

http://www.youtube.com/watch?v=NB1aCBId6qA&eurl=http%3A%2F%2Fvideo.google.com%2Fvideosearch%3Fq%3Dboyles%2520law
%26oe%3Dutf-8%26rls%3Dorg.mozilla%3Aen-US%3Aofficial%26client%3Dfirefox-a%26um%3D1%26ie%3DUTF-
8%26sa%3DN%26h&feature=player_embedded
http://www.youtube.com/watch?v=J_I8Y-i4Axc&feature=related
Charles Law: Temperature and Volume (constant P, n)
All matter expands when heated, but gases are special in that
their degree of expansion is independent of their composition.
When pressure is held constant, the volume of a gas changes
1/273 of its value for every degree oC.
-273.15 °C is absolute zero

Lower, S. (2010) Retrieved September 6, 2016 from:
http://www.chem1.com/acad/webtext/gas/gas_2.html
http://www.youtube.com/watch?v=IkRIKGN3i0k
Avogadro's Hypothesis: Moles and Volume
(constant P, T)
The same number of gas molecules will
occupy the same volume (under constant
pressure and temperature.)
http://isite.lps.org/sputnam/chem_notes/UnitVI_Gases.htm
Ideal Gas Law
# 1'
% Boyle V∝ %
P% R is the universal gas constant
% nT
$Charles V ∝ T ( V ∝
% % P J
% Avagadro V ∝ n % = 8.314
K mol
& )
nT
V=R L atm
P = 0.08206
K mol
PV = nRT
€
€
€
When MW matters….
1) Density 3) Graham’s Law

m n(MW ) P(MW )
d= = =
V V RT MW rate time
mol A
2) vrms Rate A time A MWB
= =
RateB molB MWA
3RT timeB
MW
And when it doesn’t….

PV = nRT
4) How does density relate to PV=nRT?
What the gas particle is matters….and not just
how many of them.
The density of a noble gas is 2.71 g/L at 3.00
atm and 0oC. Identify the gas.
Molecules can be identified using molar mass (MW)
5) Diffusion
Diffusion is the gradual dispersal of
one substance through another
substance.
(smells “spread” via mixing of gases)
HCl(g) air NH3(g)
Diffusion can also occur in liquids

(and to some extent in solids)
Williams, Jim. “Diffusion of a Dye in Hot and Cold Water.”Introductory
Biology I. Accessed August 27, 2010.
http://faculty.southwest.tn.edu/jiwilliams/diffusion_of_a_dye_in_water.htm
5) Effusion
Effusion is the process of gas
particles escaping a container
through a small (molecular-sized)
hole into a relative vacuum
Effusion. Retrieved September 6, 2016 from http://www.kentchemistry.com/links/GasLaws/GrahamsLaw.htm
Constant P
High P to low P
TutorVista.com.”Graham’s Law of Diffusion.” Accessed August 27, 2010.
http://www.tutorvista.com/content/chemistry/chemistry-iii/matter-states/grahams-law.php
Effusion and Molar Mass
Time required for 25 mL samples of gases to
effuse vs. square root of molar mass.
time ∝ MW
Retrieved September 6, 2016 from

http://chemed.chem.purdue.edu/genchem/history/grahamslaws.html
Graham’s Law MW rate time
At constant temperature, the rate of effusion (or diffusion) of a gas

is inversely proportional to the square root of its molar mass (MW).
Use same conditions; compare times for same # of moles effused

molA
RateA timeA timeB MWB
= = =
RateB molB timeA MWA
timeB
1 1
effusion rate ∝ α
time MW
Effusion can be used to separate (enrich) one gas from another
6) How fast are gas molecules moving?
Root mean squared velocity
Consider 1) vx, 2) the number of particles of a gas that
collide with a given area of a wall of a container in a
given period of time, and 3) the resulting momentum
change of the collision, and you get the following
relationship*:
3RT
vrms =
MW
What is vrms of helium particles in a container at 10oC?
Derivation see: http://www.chem1.com/acad/webtext/gas/gas_5.html

Problem
What is vrms of helium particles in a container at
10oC?
3RT J
vrms = = 3* 8.314 * 283K J
Kmol = 1764.6
MW g g
4
mol
kgm 2 1000g
€ s 2 kg
= 1764.6 *
€ g
m2
= 1764600 2
€ s
m mi
= 1330 ≈ 3000
s h
€
Maxwell Distribution of Speed
A gas has a distribution of kinetic energies and thus speeds
Most probable
3RT
Average vrms =
MW
Asymmetric, with no theoretical upper limit
Ian Blokland, Wave Motion, Sound, Heat, and Optics. OpenStax CNX. Feb 24, 2014 http://cnx.org/contents/7b178a67-6c06-4014-9023-0be683591a15@2.8.
http://cnx.org/contents/7b178a67-6c06-4014-9023-0be683591a15@2.8:26/Kinetic-Theory-Atomic-and-Mole (accessed Sept 13,2015)
Distribution and vrms vary with T
3RT
vrms =
MW Same MW
Higher vrms; higher rate effusion
Higher vrms @ higher T
1 2
E k = mv rms
2
Ek is higher @ higher T
Higher temperature, broader distribution, higher speed

€
Lower, S. (2010) Retrieved September 6, 2016 from http://www.chem1.com/acad/webtext/gas/gas_5.html
Distribution and vrms vary with MW
3RT
vrms =
Same Temperature MW
Higher MW, narrower distribution, lower vrms https://www.youtube.com/wa

http://www.humboldt.edu/~rap1/ChemSupp/Images/Boltz_Dist_Wiki.jpg tch?v=YgGik5q1JSA
Where do the two gases meet?
HCl NH3
Why did it take so long for the HCl(g) (vrms = 458 m/s)
and NH3(g) (vrms = 661 m/s) to travel down the tube?
1 molecule N2 at 20oC and 1 bar
vrms = 510 m/s (1100 mi/h)
Mean free path Collisions every 6.6x10-8 m

-average distance
particle travels in
between collisions
m
510
s collisions
9
collision freq = = 7.7x10
m
−8 s
6.6x10
collision
http://www.iesl.forth.gr/research/laser/biomedical/BioPhysics/images/clip_image001.gif
Collision Frequency
What two factors affect collision frequency?
1. vrms
2. Particle density
7) Mixtures The total pressure from a
mixture of gases is the
sum of the pressures of
the individual components
Ptotal = P1 + P2 + P3 + ...
" RT %
Ptotal = n total $ '
#V&
" RT %
P1 = n1$ '
#V&
In a mixture of gases,
[Figure 5.8.1 Demonstration of Dalton’s Law]. volume and temperature
Retrieved September 6, 2016
€ are constant, so pressure
fromhttps://legacy.etap.org/demo/chem5/kep depends on moles
40.jpg
Mole " nx % 4
Fraction X red = $ '=
# n total & 4 +36
= 0.1
n1 " ny % 36
X1 = X yellow = $ ' = = 0.9
n 1 + n 2 +n 3..... = (n total ) # n total & 4 +36
X red + X yellow = 0.1+ 0.9 = 1
X 1 + X 2 + X 3.... = 1
€ Xred = 0.5
Xred = 0.9
P 1 = X 1 Ptot
8) Real Gases STP: 0oC and 1 atm **We use SATP 298K, 1bar
Molar Volume Vm : the volume (of a flexible container)

occupied by 1 mole of gas at @STP = 22.4L
Gas Molar
Volume
(L/mol)
He 22.435
H2 22.432
Ne 22.422
[The gas laws and ideal gas equation].
Ideal 22.414 Retrieved January 8, 2018 from
http://pegasus.cc.ucf.edu/~jparadis/chem
Ar 22.397 2046/outline10b.html
N2 22.396
O2 22.390
CO 22.388
Cl2 22.184
NH3 22.079
Gases act more ideally @ high temperatures
Gases @ high T: Gas Condensation
• are farther from condensation point (oC)
• experience fewer IMF Ideal None
He -268.9
H2 -252.8
Ne -246.1
Ar -185.9
N2 -195.8
O2 -183.0
CO -191.5
Cl2 -34.0
NH3 -33.4
Clark, J. (2010) Real Gases. Retrieved January 8, 2018 from https://www.chemguide.co.uk/physical/kt/realgases.html
Kinetic Theory of Gases: Assumptions
-gases are composed of a large number of round particles
moving constantly and randomly
-these particles move in a straight line until they collide with

another particle or the walls of a container
-collisions between gas particles or the sides of the container

do not affect the energy of the particles
-*most of the volume of a gas is empty space; gas molecules

are infinitesimally small points “b”
-*there is NO force of attraction (IMF) between gas particles or

between the particles and the walls of the container “a”
Compression Factor (Z) Vm, actual
Z=
Hold n and T constant, vary P; measure V Vm,ideal
Vm,actual= measured molar volume
Vm,ideal = calculated molar volume
For ideal gases, Z = 1

€ “b”
@ higher pressures:
Z Z > 1, Vm, actual is larger than ideal
Volume of particles fills container;
to keep from condensing,
molecules expand
400 atm divide

@ Lower pressures:
“a” Z < 1, Vm, actual is smaller than ideal
attractive forces reduce volume Lower, S. (2010). Retrieved September 6, 2016 from
http://www.chem1.com/acad/webtext/gas/gas_6.html
Intermolecular (Attractive “a”) Forces
Considered at low T and moderate pressure (1-400 atm)
IMF kJ/m note

ol
Ion-ion 250
Hydrogen bond 20 Molecules must have H-F, H-O,
or H-N bond
Dipole-dipole 2
van der Waals 2
(induced dipole)
Figure 5.29 CHEMICAL PRINCIPLES|ATKINS|JONES|LAVERMAN ©2013

W. H. FREEMAN AND COMPANY
Attractive Forces (a)
nRT Square arises because force requires 2
P= − attraction
V particles in the same place
2
"n%
attraction = a $ '
#V &
n/V is probability of a particle
larger a, larger attractive forces being in a given place
This correction does not account for

electrostatics (full positive or a (L2 bar)/(mol2)
negative charges); it is strictly
attractive ammonia NH3 4.170
water H2O 5.536
Carbon dioxide O=C=O 3.640
Oxygen O=O 1.382
Hydrogen H-H 0.2476
Source: Weast. R. C. (Ed.), Handbook of Chemistry and Physics
van der Waals (induced dipole) < dipole/diploe <H-bonding (53rd Edn.), Cleveland:Chemical Rubber Co., 1972.
Particles have a volume (b)
Considered at high P > 400 atm
Ideal Reality Check

nRT nRT
V= There is a minimum V= + Vmin
P P
volume for a gas:
if T = 0, then V = 0 if T = 0, then V = Vmin
b (L/mol) Vmin = nb
ammonia NH3 0.0371 n the number of moles
water H2O 0.03049
b "molar volume" (L/mol)
Carbon O=C=O 0.04267
dioxide Volume of the gas particles
Oxygen O=O 0.03186 themselves (no empty space)
Nitrogen N2 0.0387
Hydrogen H-H 0.02661 Source: Weast. R. C. (Ed.), Handbook of Chemistry and Physics
(53rd Edn.), Cleveland:Chemical Rubber Co., 1972.
Topic 2: work (w) and heat (q)
1. Work
Work
Against a
Isochoric Isothermal
constant
pressure w=0
w = -PDV 2. Heat
Expansion Compression
Adiabatic
q=0
Irreversible reversible
Isothermal Phase change ;
heat
q = -w no change in T
3. The first law of thermodynamics Change in T?

State functions q = nCDT
For a closed system, DU = q + w
Energy: the potential or capacity to move
matter (to do work)
Kinetic energy (Ek): energy associated with an object by
virtue of its motion Ek = 1/2 mv2
Temperature reflects average kinetic energy
Potential energy (EP): energy an object has by virtue of its
position in a field of force Ep = mgh
Intermolecular forces (IMF)/covalent or ionic bond
***associated with phase change
Internal energy (U): Sum of kinetic and potential energies

of particles
Law of conservation of energy: total quantity remains

constant, only converted from one form to another
Surroundings: everything except the system
Isolated System:
- no exchange of matter
or energy
The internal energy (U) of an isolated system is constant.

Open and Closed Systems:
-exchange of matter and/or energy
Matter
Internal energy (U):
Sum of kinetic and potential
energies of particles Energy Energy
U = ( Σ(KE1 + KE2 +....)) +( Σ(PE1 + PE2 +....))

Change in matter changes U; each particle
has its own KE and PE
Work and heat are pathways for adding/taking

away KE and PE and thus changing U
DU: change in internal energy
Closed: DU = q+w
Work (w) and heat (q) are pathways for adding/taking

away KE and PE and thus changing U
system gains energy system loses energy

compression expansion
w > 0, + w < 0, -
Heat in Heat out

q >0 (+) q < 0 (-)
Endothermic Exothermic
The connection (or lack there of) between U and T
Matter
A change in the amount of
matter may or may not affect T
Energy
and will always affect U Energy
ΣKE1 + KE2 + KE3 +.....

T=
n(# particles)
U = ( Σ(KE1 + KE2 +....)) +( Σ(PE1 + PE2 +....))
A change in energy (constant #particles)

Changes in KE affect T and U;
Changes in PE* do NOT affect T but affect U
*(breaking/making IMF, phase changes)
Work: motion against an opposing force
Type of work Formula units
expansion -PexDV Pa*m3 = (kg/ms2)*m3= J
Raising weight mgDh kg*(m/s2)*m=J
electrical DE*q V*C=J

Potential * charge
1 J = 1 (kg m2)/s2
1 J = beat of human heart = energy to raise a small apple 1 m off of floor
Gas Expansion/Compression Work
Work = force * distance
= Pex*A*Dh
w = -PexDV DV = Vf - Vi
Sign of work indicates energy

perspective of system
Expansion
Work done by system/
Retrieved September 6, 2016 fromhttp://2012books.lardbucket.org/books/-01-
thermodynamics-and-work.html
on surroundings
system loses energy
Compression:
(Vf >Vi) (w < 0) (w -)
work done on system/
by surroundings
system gains energy
(Vf < Vi ) (w > 0 ) (w +)
“Iso” terms
1) Constant P (Isobaric) w = -PexDV
Flexible containers: (e.g., a balloon OR a cylinder with a
movable piston)
2) Constant V (Isochoric) w = 0
Rigid containers
Pressure of a latex balloon as it is inflated

3) Constant T (Isothermal) https://www.youtube.com/watch?v=fwh-i0WB_bQ
(accessed Sept 2015)
http://scipp.ucsc.edu/outreach/balloon/labs/InflationExp.htm
Isobaric work (Constant P/change V,T)
1.2
P = 1 atm
1
0.8
Pressure (atm)
0.6
0.4
0.2
0
0 5 10 15 20 25
Volume (L)
V starts at 2.24 L and expands to 22.4 L against an external pressure

of 1 atm by increasing T
w = -PextDV = -1atm* (22.4-2.24)L = -20.16 L atm
1 L atm = 101.325 J
Isothermal Expansion
Energy lost = area under PV curve = nRTln(Vf/Vi)
Reversible: (theoretical) one area (infinite
P
number of steps): All of the energy lost by
system is converted to work.
# Vfinal &
V w = −nRT ln% (
$ Vinitial '
Irreversible: (2 areas) (actual) System

loss of potential work loses energy equivalent to area under
P € work the PV curve. Some is converted to
work. Some lost as friction, etc.
w = -PexternalDV
V
Isothermal, Reversible Expansion
(infinite number of steps)
w = −PextΔV
−nRTΔV
w=
V
Vfinal
ΔV
w = −nRT ∫
Vinitial V
# Vfinal &
w = −nRT ln% (
$ Vinitial '
€
OpenStax College, Physics. OpenStax CNX. http://cnx.org/contents/031da8d3-

€ b525-429c-80cf-6c8ed997733a@9.30.
Isothermal, Irreversible Expansion
w = -PexDV = -1atm*(20L-1L) = -19 L*atm
Pushing against only a single external pressure
Pi = 20 atm
Vi = 1 L 20
Pex = 1atm
15
Pressure
10
expansion
5
isothermal
expansion
0
0 5 10 15 20
20 atm 1 atm Volume Pf = 1 atm
Vf = 20 L
1L 20 L
Isothermal Compression:
System must gain energy equal to the area under curve
Reversible: One area: the area under the curve
equals the work energy done on the system and the
work energy lost by the surroundings.
P
The surroundings apply pressure in infinitely small
increments. #
Vfinal &
V
w = −nRT ln% (
$ Vinitial '
Irreversible: The energy from the surroundings is

broken into two parts: a) lost energy and b) the work
a energy gained by the system.€ # Vfinal &
P w = −nRT ln% (
$ Vinitial '
b How do the surroundings do irreversible work? They
compress the system using a single pressure equal to
V the desired final pressure of the system. The system
cannot gain all of this energy and remain at the same
temperature. €
Work
Against a
Isochoric Isothermal
constant
pressure w=0
w = -PDV
"V %
w = −nRT ln $ 2 '
Expansion Compression # V1 &
Irreversible reversible
" V2 % Adiabatic
w = −nRT ln $ '
# V1 & q=0
Free expansion:
no work done against a Isothermal Phase change ;
vacuum, Pext = 0 heat
q = -w no change in T
1 L atm = 101.325 J
Change in T?
q = nCDT
Notes on q
Adiabatic: no heat exchanged with surroundings
q = 0 (think insulated container or very fast process)
If heat is added to a system (q > 0):

1) heat could be used to increase KE in all forms:
translational, vibrational, and rotational and to raise the
temperature q = nCDT
2) all heat could be transferred into work; there would
be no change in temperature if q = -w (aka isothermal)
3) heat breaks IMF and changes the PE of the system
(ie phase change)
PE goes up so U goes up
KE does not change so T constant
Notes on q
1) heat could be used to increase KE in all forms:
translational, vibrational, and rotational and to raise the
temperature q = nCDT*
Cp,m = Cv,m + R
Why is Cp,m > Cv,m?
*Only use q = nCDT when there is a temperature change

Notes on q
2) all heat could be transferred into work; there would
be no change in temperature if q = -w (aka isothermal)
Isothermal, closed dU = q+w = 0
6
2 q (heat)
0 w (work)
q w
-2
-4
-6
w q
3) heat breaks IMF and changes the PE of the system

(ie phase change)
PE goes up so U goes up
KE does not change so T constant
Quiz question
In the figure, the volume at point "c" is 800 L and
the pressure is 2 atm. The volume at "a" is 400 L and
the pressure is 4 atm. What is the total work as the
system goes through one complete cycle
a b c d a?
A) -800 L*atm
B) 800 L*atm
C) 0 L*atm
D) -2400 L(atm
E) 2400 L*atm
State Function
Energy (U) is a state function -it depends only on the state
and not how it got there (so are T, P, V, S, and H)
Both w and q DO depend on the path taken. They are NOT state functions
Alternatively, both work and heat reflect a change in the system, not an
absolute amount of a property…you cannot have work without a change in
volume; you cannot have q without a change in T or w.
Topic 03 Enthalpy
1) Enthalpy defined
2) qin = -qout (heat transfer/energy is conserved)
3) Bond making/breaking
4) Combustion
5) Thermochemical Equations (heat is stoichiometric)
6) Hess’ Law (H is a state function)
7) Formation (a new reference point)
8) Phase changes (make/break IMF)
1) Enthalpy (H)
Create a state function for reactions taking place @ constant
P .…liquid and solid reactions experience very small volume
changes against a constant external pressure of 1 bar.
@ constant P
define: DH = DUP + PDV
sub in DUP = qP + wP
DH = qP + wP + PDV
sub in wP = -Pex DV
DH = qP - Pex DV + PDV
assume open
DH = qP container so –PexDV +
PDV = 0
DH = qP …when there is constant P and a change in T
DH = nCP,mDT
For solids and liquids, CV,m ~ CP,m; no ideal values

Cs specific heat (capacity) Cm molar heat capacity
q = mCsDT q = nCmDT
Specific heat Molar heat

(J/goC) Cs capacity Cm
(J/moloC)
Water 4.184 75.3 Or K
Ethanol 2.43 112.2
Aluminum 0.901 24.3
Cs*MW = Cm
2) qin = -qout Cs,steel = 0.5 J/goC
aka Energy is conserved Cs,concrete = 0.10 J/goC
A steel rod (mass 10 g) is heated to 75oC. The rod is set on

a 20 g block of concrete that is at 25oC. When the two
materials come to thermal equilibrium, what is their
temperature? Steel, 10 g, T =75oC, C =0.5J/goC
i s
Concrete, 20 g, Ti =25oC, Cs=0.1J/goC
Kinetic energy transfer

Cs,steel = 0.5 J/goC
qin = -qout Cs,concrete = 0.10 J/goC
A steel rod (mass 10 g) is heated to 75oC. The rod is set on
a 20 g block of concrete that is at 25oC. When the two
materials come to thermal equilibrium, what is their
temperature? Steel, 10 g, T =75oC, C =0.5J/goC
i s
Concrete, 20 g, Ti =25oC, Cs=0.1J/goC
qsteel = −qconcrete
msteel * Cs,steel * ΔTsteel = −mcon * Cs,con * ΔTcon
J J
10g * (0.5 o€ ) * (Tf − 75 C) = −20g * (0.1 o ) * (Tf − 25 o C)
o
gC gC
€ 5Tf − 375 = −2Tf + 50
Tf = 60.7 o C
3) Bond making/breaking reaction
DH is always negative for making a bond

DH is always positive for breaking
One side: atoms in gas phase
One side: substance with 1 type of bond in gas
phase
H2(g) ® 2H(g) DHo = +436 kJ break bond
N(g) + 3H(g) ® NH3(g) DHo = -1164 kJ

makes 3 N-H bonds
1 N-H bond = -1164/3
= -388 kJ
Bond Enthalpy (kJ/mol)
(average energy needed to break bonds
into atoms in the gas phase)
H-F 566 C=C 598 C-O 336

H-Cl 431 C=N 418 C=O 695
H-Br 366 C=O 695-803 C≡O 1073
H-I 299
C-Si 301 C-C 356 C-C 356
C-P 264 C-N 285 C=C 598
C-S 272 C-O 336 C≡C 813
C-Cl 327 C-F 486
note bond enthalpy (+) is usually given, need to reverse sign
for bond formation
Holy Contradiction Batman!
It takes energy to break
bonds….and yet we get energy
from fats (and carbohydrates and
alcohol) by breaking them down
???
Food is broken down by adding

O2 and converting all of the
carbon and hydrogen in the food
molecules to CO2 and H2O.
Energy from Ethanol
CH3CH2OH + 3 O2 → 2 CO2 + 3 H2O
H H
O
H C C O H + 3 O O 2 O C O + 3 H H
H H
moles Bonds Enthalpies kJ moles Bonds Enthalpies

broken kJ/mol made kJ/mol
5 C-H 416 2080 4 C=O 803 3212
1 C-C 356 356 6 O-H 467 2802
1 C-O 336 336
1 O-H 467 467
3 O=O 498 1494
Total 4733 6014
(+) bond breaking (-) bond making
Breaking Down Ethanol
4733 kJ into reactants 6014 kJ out of

products
Δ Hrxn = + 4733 kJ - 6014 kJ

= -1281 kJ
Conversion to food Calories
1 Calorie = 1 kilocalorie = 1000 calories
1 calorie = 4.184 J
For ethanol
1281 kJ 1000J 1 cal 1Cal
mol 1 kJ 4.184 J 1000 cal = 306 Cal/mol
306 Cal 1 mol CH3CH2OH

mol ethanol 46 g = 6.7 Cal/g
Comparing Energy Sources
Bond Nutritional
Energy Guidelines*
Ethanol 6.7 Cal/g 7 Cal/g
Glucose 3.8 Cal/g 4 Cal/g

Stearic 8.9 Cal/g 9 Cal/g
Acid
C18H36O2 + 26 O2 18 CO2 + 18 H2O DH = -10622 kJ

Stearic acid
*http://www.unlimited-health.com/nutrition/
4) DHoc combustion
Combustion (burn in oxygen)
o SATP (298K, 1bar)
Generally a negative DH
Reactants: 1 mole of substance + O2(g) à
Products: à CO2(g) + H2O(?) +…
H2O(l) @25oC is high heat value (more negative DH)
H2O(g) is lower heat value
C5H12(l) + 8 O2(g) ® 5 CO2(g) + 6 H2O(g) DH = -3345 kJ

C5H12(l) + 8 O2(g) ® 5 CO2(g) + 6 H2O(l) DH = - 3509 kJ
C12H22O11(s) + 12 O2(g) ® 12 CO2(g) + 11H2O(g) DH = -5654 kJ

5)Thermochemical Equations
(Heat is Stoichiometric)
A calorimeter containing 739 grams of water as its only
heat source/sink is used to measure the heat of combustion
of 0.303 g of sucrose (C12H22O11 MW = 342 g/mol). The
temperature increase was found to be 1.62oC. Calculate the
DH of the reaction.
Constant volume:
measures DU = qv
Constant pressure:
measures DH = qp
Assume constant pressure

qrxn = -qcalorimeter
Calorimeter Cs,H2O = 4.184 J/goC
A calorimeter containing 739 grams of water as its only heat
source/sink is used to measure the heat of combustion of
0.303 g of sucrose (C12H22O11 MW = 342 g/mol). The
temperature increase was found to be 1.62oC. Calculate the
DH of the reaction.
DH = qrxn = -qcalorimeter
= -mCH2O DT
= -739g (4.184 J)(+1.62oC)
goC
= -5009 J
−5009J 342g sucrose " 1kJ % −5654kJ
* *$ '=
0.303g sucrose mol sucrose # 1000J & mol sucrose
Heat is stoichiometric
C12H22O11(s) + 12 O2(g) ® 12 CO2(g) + 11H2O(g) DH = -5654 kJ
Thermochemical Equations
3C(s,graphite)+ 4H2(g) → CH3CH2CH3 (g) DH = - 103.82 kJ

−103.82kJ 4molH 2 −103.82kJ
3molC −103.82kJ 1molCH 3CH 2CH 3
6C(s,graphite)+ 8H2(g) → 2CH3CH2CH3 (g) DH = - 207.64 kJ
Double stoichiometric coefficients, double DH.
CH3CH2CH3 (g) → 3C(s,graphite)+ 4H2(g) ΔH = +103.82 kJ

(reverse reaction; change sign of DH)
6) Hess’s Law (DH is a state function)
Hess’s Law of heat summation: For a chemical equation
that can be written as the sum of two or more steps, the
enthalpy changes for the overall equation equals the sum
of the enthalpy change of individual steps
A B C D
A®B + B®C + C®D = A®D
H2(g) + 1/2 O2(g) ® H2O(g) DH1 = -241.8 kJ

H2O(g) ® H2O(l) DH2 = -44.0 kJ
_____________________________________
H2(g) + 1/2 O2(g) ® H2O(l) DHrxn = -285.8 kJ
Find the DHrxn:
1) Multiply the entire equation (including DH)
2) Flip equation (turn it in the opposite direction); change sign of DH)
CH3CH2CH3 (g) + 5 O2(g) → 3 CO2 (g) + 4 H2O (g)
3C(s,graphite)+ 4H2(g) → CH3CH2CH3 (g) DH = - 103.82 kJ

C(s,graphite)+ O2 (g) → CO2 (g) DH = - 393.5 kJ
H2(g) + ½ O2(g) → H2O(g) DH = - 241.82 kJ
CH3CH2CH3 (g) → 3C(s,graphite) + 4H2(g) DH = (-) -103.82 kJ

3C(s,graphite)+ 3O2 (g) → 3CO2 (g) DH = (3) - 393.5 kJ
4H2(g) + 2 O2(g) → 4 H2O(g) DH = (4) -241.82 kJ
DH = -2044 kJ
H is a state function; we only care about the
difference in enthalpy (DH) and not what
Hinitial or Hfinal are so we can set a zero point
anywhere. Substance DH (kJ/mol) o
f
Al(s) 0
Al+3(aq) -524.7
1. For bond enthalpies, the zero Al2O3(s) -1675.7
point is gaseous atoms Al(OH)3(s) -1276
AlCl3(s) -704.2
2. For formation, the zero point is Br2(l) 0
elements in standard states Br2(g) +30.91
C(s,graph) 0
Standard State = Element at SATP C(s,diamond) +1.895
ie: H2(g), Br2(l), C(s,graph) C(g) +716.68

CO(g) -110.53
CO2(g) -393.51
7) Formation reactions
Reactants: elements in their standard state”
Products: one mole of a substance
May have a negative OR positive DH
C(s,graph)+ ½ O2(g)+ N2(g) + 2H2(g) → CO(NH2)2(s)

DHo = -333.5 kJ
DHof(urea)
ΔHof elements in standards state = 0

ΔHof found in table on Canvas
Find the DHrxn using formation
CH3CH2CH3 (g) + 5 O2 (g) → 3 CO2 (g) + 4 H2O (g)
From Data Tables

CH3CH2CH3 (g) DHof = - 103.82 kJ/mol
CO2 (g) DHof = - 393.5 kJ/mol
H2O(g) DHof = - 241.82 kJ/mol
ΔHorxn = Σ nDHof products - Σ nDHof reactants

DHorxn =[3 mol CO2(-393.5 kJ/mol) + 4 mol H2O(-241.83 kJ/mol)]
-[1 mol propane(-103.82 kJ/mol) + 5 mol O2 (0 kJ/mol)]
= -2147.82 kJ - (-103.82 kJ)

= -2044 kJ
Bond Enthalpies vs. Formation
CH3CH2OH(g) + 3 O2(g) → 2 CO2(g) + 3 H2O(g)

estimate or
DH = -1281 kJ from bond enthalpies “average”
CH3CH2OH(l) DHof = - 235.3 kJ/mol

direct
CO2(g) DHo f = - 393.5 kJ/mol measurement;
H2O(g) DHof = - 241.82 kJ/mol more accurate
Δ Horxn = Σ nDHof products - Σ nDHof reactants

Δ Horxn = -1277
bond making/breaking
atoms in the gas phase

ie O(g), Br(g)
Reactants
products
elements in standard state

ie O2(g), Br2(l)
formation
How to find DHorxn
1. Bond enthalpies
DHrxn = S(H to break reactant bonds) – S H
(from making product bonds)
2. Calorimeter (measure directly)
3. Hess’ Law (use known thermochemical
equations)
v Multiply equations, multiply DH
v Flip equations, flip sign of DH
v Add equations, add DH
4. Formation
Δ Horxn = Σ nDHof products - Σ nDHof reactants
8) Phase change: potential
energy of intermolecular forces
Intermolecular forces
Encyclopedia Britanica “phase change”

http://www.britannica.com/EBchecked/media/155241/Sublimation-deposition-
condensation-evaporation-freezing-and-melting-represent-phase-changes
Covalent bond Accessed Jan 2014.
only potential energy change;

U changes, but T does not
Encyclopedia Britannica (2016). [Online image] Retrieved September 13, 2016 from:
https://www.britannica.com/science/internuclear-separation
Solid <-> Liquid Constant P
Constant T, Tmelting or Tfusion
Break IMF, q >0

melting
freezing
Make IMF, q < 0
DHfus: enthalpy of fusion

q = ±nΔH fus latent heat of fusion
specific melting heat
Encyclopedia Britanica “phase change” http://www.britannica.com/EBchecked/media/155241/Sublimation-deposition-condensation-
evaporation-freezing-and-melting-represent-phase-changes Accessed Jan 2014.
Liquid <-> Gas Constant P
Constant T, Tboiling
Break IMF, q >0, w < 0
evaporation
condensation
Liquid Make IMF, q < 0, w > 0 Gas
q>w
q = ±nΔH vap DHvap: enthalpy of vaporization

Substance DHfus Melting point DHvap Boiling point
(kJ/mol) (K) (kJ/mol) (K)
Ne 0.33 24 1.80 27
O2 0.44 54 6.82 90.2
CH4 0.94 90.7 8.18 112
C2H6 2.85 90.0 14.72 184
Cl2 6.40 172.2 20.41 239
CCl4 2.67 250 30 350
H2O 6.01 273.1 40.657 373.1
Data from:
http://chempaths.chemeddl.org/services/chempaths/?q=book/Quick%20Resources/1251/tabl
e-molar-enthalpies-fusion-and-vaporization Accessed Sept 12, 2016
Phase changes enthalpies
What’s wrong with this figure???
DHvap
evaporation q = n DHvap
condensation q = -nDHvap
DHfus
melting q = n DHfus
freezing q = -n DHfus
DHsub = DHfus + DHvap
DHvap > DHfus [Online image]. Retrieved September 13, 2016 from
https://saylordotorg.github.io/text_general-chemistry-principles-
patterns-and-applications-v1.0/s15-05-changes-of-state.html
Phase changes
Heating Curve occur at constant
P, so DH is
relevant
For water from -20oC to 110oC
q=mCs,steamDT
110oC
vaporization q = nDHvap
Temperature (oC)
100oC
q=mCs,waterDT Phase changes

occur at constant
melting q = nDHfus T, heat energy
0oC used to break IMF
(potential)
-20oC q=mCs,iceDT
q added
Cooling Curve
water from 110oC to -20oC
q=mCs,steamDT
110oC
Temperature (oC)
condensation q = -nDHvap 1
100oC
2
3 q=mCs,waterDT
0oC 5 freezing q = -nDHfus

4
-20oC q=mCs,iceDT
q added
Topic 4: Entropy and Gibbs
1) Microstates
2) What changes entropy?
3) Comparing molar entropy
4) Calculating changes in entropy
5) Residual entropy
6) Laws of thermodynamics
7) Gibbs defined
8) How DH, DS and T affect spontaneity
9) Thermodynamically stable compounds
1) What is Entropy?
Entropy = “disorder”
Entropy = measurement of probability
Low entropy Natural progression High entropy
High order High disorder
Low probability High probability
Entropy is a measure of the degree of spreading

and sharing of thermal energy within a system.
The energy of the system is more dispersed when

the number of possible microstates is greater.
Energy Quantization
Energy is quantized not continuous
Recall energy levels of electrons
O O O
H H H H H H
O O O
H H H H H H
stretching change in
bond angle
Microstate: a snapshot showing the exact
distribution of all of the specific (distinguished)
molecules on specific energy levels at one
instant in time
Example: 3 particles in a system with a total energy of 3
Note: Distinguish between particles
more microstates = higher Entropy

http://www.chem1.com/acad/webtext/thermeq/TE1.html#SEC3
Entropy (S)
At a given temperature and
volume,
S = kB ln W
W = # microstates
kB (Boltzmann constant) = R/NA
kB = 1.4 x 10-23 J/K
6 particles with an energy of 9
# of Each box is a configuration
microstates
w/i each
configuration
http://hyperphysics.phy-astr.gsu.edu/HBASE/quantum/disbol.html
Systems ……
with a higher T
that melt or evaporate
with more matter
that increase volume
with a higher molar mass
…..have a higher entropy.

Energy
Temperature & Entropy
Energy
Low T High T
more microstates
higher entropy
Increased thermal energy makes additional

energy levels and thus additional microstates
accessible resulting in an increase in entropy (S)
Temperature & Entropy
A greater distribution
of vrms indicates a
greater distribution of
kinetic energy (1/2
mv2) and an increase
in entropy
Lower, S. (2010) Retrieved September 6, 2016 from http://www.chem1.com/acad/webtext/gas/gas_5.html

Temperature S
Phase Change (J/K)
& Entropy
T (K)
Great DS at lower T
Upon melting and vaporizing, the molecules of solids,

liquids, and gases have increasingly greater freedom to
move around, facilitating the spreading and sharing of
thermal energy. Phase changes are accompanied by
massive and discontinuous increase in the entropy.
Matter & entropy
3 particles with a total energy of 3 leads to
4 particles with an energy of 3 leads to:

Config i (3 •@ 0; 1 •@3): 4 microstates
Config ii (2 •@ 0; 1 •@1; 1 •@2): 12 microstates
Config iii (1 •@ 0; 3 •@ 1): 4 microstates
20 microstates
Volume, Molar mass, & Entropy
An increase in volume or molar mass increases entropy
because energy levels become closer together and thus more
energy levels are accessible at the same T.
2 2
n h
En =
Energy
Energy
8ml 2
same T
n = 0, 1, 2, 3, 4, etc.
Small volume Larger volume
(a quantized energy level) fewer microstates

less entropy
more microstates
higher entropy
h = Plank’s constant Increase in V, increase #

accessible energy levels
m = mass (molar mass)
l = length (proportional to volume)
Figure 5.27 CHEMICAL PRINCIPLES|ATKINS|JONES|LAVERMAN ©2013 W. H. FREEMAN AND COMPANY
Keep length (volume) constant;
compare mass = 1 or 2
mass = 1 mass = 2
n 2h 2 n 2h 2
En =
8ml 2
En =
8ml 2
02 h 2 " h2 % 02 h 2 " h2 %
Eo = 8(1)l 2 = 0$ 2 '
# 8l &
Eo = 8(2)l 2
= 0$ 2 '
# 8l &
12 h 2 " h2 % 12 h 2 1 " h2 %
E1 = 8(1)l 2
= 1$ 2 '
# 8l &
E1 = 8(2)l 2
= $ 2'
2 # 8l &
22 h 2 " h2 % 22 h 2 " h2 %
E2 = 8(1)l 2
= 4$ 2 '
# 8l &
E2 = 8(2)l 2
= 2$ 2 '
# 8l &
32 h 2 " h2 % 32 h 2 " h2 %
E3 = 8(1)l 2 = 9$ 2 '
# 8l &
E3 = 8(2)l 2
= 4.5$ 2 '
# 8l &
42 h2 " h2 %
E4 =
8(2)l 2
= 8$ 2 '
# 8l &
3) Standard Molar Entropy
Entropy (Som) J
K mol
solid < liquid < gas

H2O(l) = 109.6 H2O(g)= 188.83
lighter < heavier

substance substance
B(s) = 5.86 Al(s) = 28.33
Principles of General Chemistry
[online image] Retrieved less complex < more complex
September 15, 2016 from
http://2012books.lardbucket.org/b
ooks/principles-of-general-
chemistry-v1.0/s22-04-entropy- MW = 20 HF(g) = 173.78; D2O(g) = 198.34
changes-and-the-third-.html
4) Quantifying Changes in Entropy
Energy reversibly transferred as heat at a

given temperature
qrev Use reversible q and later w.

ΔS =
T Constant temperature
Units: J/K
Entropy is a state function; path does not matter.

DS for Phase Changes
Take place at constant T
Are reversible
Constant P so q = +/- n*DH
solid ßà liquid liquid ßà gas

n* ΔH fus n* ΔHvap
ΔS = ± ΔS = ±
Tm Tb
Melting and boiling: ΔH > 0, ΔSsys > 0

Freezing and condensing: ΔH <0, ΔSsys < 0
DS Closed, Isothermal
Isothermal reversible expansion of an ideal gas

DU = 0 = q + w
V2
qrev = -wrev= - ( −nRT ln )
V1
V2
qrev nRT ln V2
ΔS = = V 1
= nRln
T€ T V1
DS Closed, Isochoric
qrev qrev = nCv,m ΔT

ΔS =
T For constant volume
€
nCv,m ΔT T2 ΔΤ T2
ΔS =
T
....nCv,m ∫ T1 Τ
= nCv,m ln
T1
T2 T2 > T1 DS > 0
ΔS = nCv,m ln T in K
T1 T2 < T1 DS < 0
1.00 mol of a monoatomic gas is compressed from
5.00 L to 1.00 L by driving in a piston. The
temperature increases 20.0oC to 25.2oC.
finish
step 2
T
step 1 start
V
1.00 mol of a monoatomic gas is compressed from 5.00 L
to 1.00 L by driving in a piston. The temperature increases
20.0oC to 25.2oC.
Step 1: Const. T Step 2: Const. V
V1 = 5.00 L; T1 = 20.0oC;
V2 = 1.00 L T2 = 25.2oC
V2 T2 3 298.2
ΔS = nRln ΔS = nCv ln = 1* * 8.314 ln
V1 T1 2 293
DS = -13.4 J/K DS = +0.22 J/K
DS2step = -13.4 + 0.22 = -13.1 J/K
DS Closed, Isobaric
T2 V2
1) Change in temperature: ΔS = nCvln T1 + nRln V 1
T2 constant P and n;
V1 nR V2
ΔS = nCv ln T1
= =
P T2
T1
T2 V2
=
T1 V1
2) Change in volume: T2 T2
ΔS = nCv ln + nRln
V2 T1 T1
ΔS = nRln T2
V1 ΔS = n ln (Cv + R)
T1
Calculate in two steps (1+2) T2
ΔS = n ln (CP )
……or use just one T1
Entropy equations:
S = kB ln W
DSsys = qrev/T (parent equation for system)
For phase change: DSsys = DH/T *provide sign
Change in V; const T: DSsys = nRln(V2/V1)
Change in T; const V: DSsys = nCv,m ln(T2/T1)
Change in T and V; const P: DSsys = nCp,m ln(T2/T1)

Standard Reaction Entropies
o
ΔSrxn = ΣnSmo ( products) − ΣnSmo (reactants)
Standard conditions: 298K, 1 bar
1/2 H2(g) + 1/2 F2(g) → HF(g) DHo = -271.1 kJ
Σ nSom products = 173.78 J/Kmol (1 mol HF) = 173.78 J/K

Σ nSom reactants = 130.68 J/Kmol (0.5 mol H2) + 202.78 J/Kmol (0.5 mol F2)
= 166.73 J/K
Δ Sorxn = Σ nSom products - Σ nSom reactants Smo DHof

= 173.78 J/K - (166.73 J/K) (kJ/mol)
(J/(Kmol)
= 7.05 J/K
H2(g) 130.68 0
F2(g) 202.78 0
HF(g) 173.78 - 271.1
Predicting the sign of DSrxn
More moles of gas,
A) H2O(l) à H2O(g) higher entropy.
B) Na(s) + H2O(l) à Na+(aq) + ½ H2(g) + OH-(aq)
C) H(g) + Cl(g) à HCl(g)
D) H2(g) + Cl2(g) à 2HCl(g)
E) CH3CH(OH)CH3(l) à CH3CH(OH)CH3(s)
Hess’ Law and rules for flipping, multiplying, and
adding equations that apply to DH apply to DS
5) Residual Entropy at 0 K
Molecule positions “identical”
The entropies of all perfect crystals

approach zero as the absolute temperature
approaches 0. (3rd Law)
S ®0 as T®0 K
S = kB ln (# microstates) = k ln (1) = 0
T goes to 0; E ® 0; # microstates ® 1
Residual Entropy at T = 0K
Positional Disorder
CO vs HCl ClO3F
Figures 9.7 & 9.8 CHEMICAL

PRINCIPLES|ATKINS|JONES|LAVERMAN
©2013 W. H. FREEMAN AND COMPANY
Unsymmetrical molecules can occupy positions differently

Stronger dipole leads to locking of position order and lower
6) The Laws of Thermodynamics
Zeroth Law: When two systems, each internally in
thermodynamic equilibrium at a different temperature, are
brought in diathermic contact with each other they
exchange heat to establish a thermal equilibrium between
each other.
First Law: DU = q + w
(internal energy of an isolated system is constant)
(energy is conserved; can take on different forms)
Second Law: DSTot = DSsys + DSsurr ≥ 0
DSTot > 0 spontaneous, irreversible
= 0 equilibrium, reversible
< 0 nonspontaneous
Third Law: S ®0 as T®0K
DS..the Big Picture
ΔStotal = ΔSsys + ΔSsurr
ΔSsys is what we have been calculating
ΔSsurr surroundings are less confined and controlled

Assumptions: Surroundings are BIG so isothermal,
constant pressure
ΔH
ΔSsurr = −
T
Total Entropy
1/2 H2(g) + 1/2 F2(g) → HF(g) DHo = -271.1 kJ ΔSo = 7.05 J/K
Smo DHof
ΔStotal = ΔSsys + ΔSsurr (J/(K mol) (kJ/mol)
J ΔH H2(g) 130.68 0
= 7.05 −
K T F2(g) 202.78 0
J " −271.1kJ % HF(g) 173.78 - 271.1
= 7.05 −$ '
K # 298K &
J 0.910kJ " 1000J %

= 7.05 − + $ '
K K # 1kJ &
J J J
ΔSTot = 7.05 + 910 = 917
K K K
Spontaneous: ΔStotal > 0 (product favored)

Reversible: ΔStotal = 0 (equally favored)
Nonspontaneous: ΔStotal < 0 (reactant favored)
7) DStot leads to Gibbs free energy
DSTot = DSsys + DSsurr ΔSsurr = −

ΔH
T
DSTot = DSsys - DH/T
Multiply by -T
-T DSTot = -TDSsys + DH
€
DGT = - T DStot
DGT = -TDSsys + DH
DSTot > 0; DGT < 0 spontaneous;

product favored
DGT = DH -TDSsys DSTot = 0; DGT = 0 equally favored
DSTot < 0; DGT > 0 not spontaneous;
reactant favored
Gibbs Free Energy
Defined at: Constant Temperature and Pressure
State function
Used to:
*Tell if process is “spontaneous” (product favored)
*Determine how temperature change affects
spontaneity (how product favored)
*Calculate non-expansion work
DGo = DHo -298K*DSo sys
DGT = DHo -TDSo sys
Assume DHo and DSo are constant with T

Calculate DGorxn
o o o
ΔG rxn = ΣnΔG f ( products) − ΣnΔG f (reactants)
Standard conditions: 298K, 1 bar, 1M

DGof standard Gibbs free energy of the reaction forming 1
mole of a substance from its elements in their standard states
DGof = 0 for an element

in its standard state
Smo DHof DGof
J/(Kmol) (kJ/mol) (kJ/mol)
H2(g) 130.68 0 0
F2(g) 202.78 0 0
HF(g) 173.78 - 271.1 -273.2
2 ways to find DGo from Appendix 2A
1/2 H2(g) + 1/2 F2(g) → HF(g) DHo = -271.1 kJ ΔSo = 7.05 J/K
Smo DHof DGof
o
ΔGrxn = ΣnΔG of ( products) − ΣnΔG of (reactants) J/(Kmol) (kJ/mol) (kJ/mol)
H2(g) 130.68 0 0
DGo = DHo - TDSo
F2(g) 202.78 0 0
HF(g) 173.78 - 271.1 -273.2
o
ΔGrxn = ΣnΔG of ( products) − ΣnΔG of (reactants)
o $ kJ ' $ 1 kJ 1 kJ '
ΔG rxn = &1molHF * (−273.2 )) − & molH 2 * 0 + molF2 * 0 )
% mol ( % 2 mol 2 mol (
o
ΔGrxn = −273.2kJ
ΔG o = ΔH o − TΔS o
J 1kJ
= −271.1kJ − 298K(7.05 ) *
K 1000J
= −271.1kJ − 2.1kJ = −273.3kJ
Gibbs Free Energy NOT @ 298K
o
ΔGrxn = ΣnΔG of ( products) − ΣnΔG of (reactants)
DGT = DHo - TDSo

*use standard DHo and DSo
2Fe2O3(s) + 3C(s) ® 4 Fe(s) + 3 CO2(g)

DHo = +468 kJ and DSo = + 558 J/K.
@200K
ΔG200 = ΔH o − TΔS o
J 1kJ
= 468kJ − 200K(558 ) *
K 1000J
= 468kJ −111.6kJ
= 356.4kJ
8) How does temperature affect spontaneity?
Will ice melt at 263 K, 273 K, 300 K?
H2O(s) → H2O(l)
ΔHofus (H2O) = 6.0 kJ/mol DH > 0
ΔSofus (H2O) = 22 J/(K mol ) DS > 0
DGT = DHo - TDSo

6.0kJ ⎛ 22J ⎞ ⎛ 1kJ ⎞
ΔG273K = − 273K ⎜
mol ⎝ Kmol ⎟⎠ ⎜⎝ 1000 J ⎟⎠
kJ
ΔG273K = (6 − 6) =0
mol
263K DG263K = + 0.43 kJ/mol solid (reactant favored) (DH > TDS)
273K DG273K = 0 kJ/mol equally favored (DH = TDS)
300K DG300K = - 1.1 kJ/mol liquid (product favored) (DH < TDS)
Energy level model
DHo < 0; DSo > 0
DGT = DHo - TDSo
- =- - (+)
C(s,graphite) + O2(g) → CO2(g)

ΔH = –393 kJ
ΔS = +2.9 J/K
ΔG = –394 kJ at 298 K
Spontaneous at all temperatures.
Positive entropy change is due mainly to the greater
mass of CO2 molecules compared to those of O2.
Lower, Simon. "Free energy: The Gibbs Function." chem 1 virtual textbook. 2007. Simon Fraser
University, Web. 28 Jan 2010. <http://www.chem1.com/acad/webtext/thermeq/TE4.html>.
DHo > 0; DSo < 0
DGT = DHo - TDSo
+ =+ -
(-)
½ N2(g) + O2(g) → NO2(g)

ΔH = 33.2 kJ
ΔS = –249 J /K
ΔG = +51.3 kJ at 298 K
Spontaneous at NO temperature.
Reverse process is spontaneous but slow so NO2 can exist
DHo > 0; DSo > 0
DGT = DHo - TDSo

?= + -(+)
N2O4(g) → 2 NO2(g)
ΔH = 55.3 kJ
ΔS = +176 J/K
ΔG = +2.8 kJ at 298 K
Spontaneous at high temperatures.
Decomposition takes energy but increases entropy
DHo < 0; DSo < 0
DGT = DHo - TDSo
?= - -
(-)
3 H2(g) + N2(g) → 2 NH3(g)
ΔH = – 46.2 kJ
ΔS = –389 J/K
ΔG = –16.4 kJ at 298 K
Spontaneous at low T
Entropy negative due to decrease in #moles of gas
Finding the transition temperature
H2O(s) → H2O(l)
ΔHofus (H2O) = 6.0 kJ/mol
ΔSofus (H2O) = 22 J/(K mol )
DGT = DHo - TDSo

Summary of Gibbs
DSTot > 0; DGT < 0 spontaneous;

product favored
DSTot = 0; DGT = 0 equally favored
DSTot < 0; DGT > 0 not spontaneous;
reactant favored
DGT = DHo -TDSo sys

How temperature affects spontanaeity depends
on signs of DHo and DSo ; this can be
represented in energy level model
o o o
ΔG rxn = ΣnΔG f ( products) − ΣnΔG f (reactants)
9) Thermodynamic Stability
Thermodynamically unstable
compound (positive DGof)
Says nothing about rate of

reaction.
Thermodynamically unstable
compounds that survive for
long periods are nonlabile or
inert.
Thermodynamically
stable compound
(negative DGof)
Topic 05: Equilibrium
1. What does the number (of DGT) mean?
2. K: the equilibrium ratio
3. K to Kc
4. Linking K to DGT
5. K, DGT and T
6. What is equal at equilibrium?
7. K and Q
8. DGtoeq
9. K, Q and ICE
10. Equilibrium response to stressors
11. Disturbance Graph
12. K and Hess’ Law
1) What does the number DGT mean?
DGT = -125 kJ vs. DGT = -25 kJ vs. DGT = +25 kJ vs. DGT = +125 kJ
Negative DGT Positive DGT
Spontaneous Not spontaneous

Thermodynamically favored Thermodynamically unfavored
Product favored Reactant favored

Fast or slow? We don’t know. Fast or slow? We don’t know
Does NOT go to completion Does NOT stay at all reactants
More products than reactants More reactants than products
Why? Mixing
The result: Equilibrium
Entropy Increases with Mixing
constant V
constant T
n S
constant n
constant T
V S
constant n
constant T
V S
gas, liquid or solid mixing V S

Mixing results in a lowering of G
The system will spontaneously act to minimize G
The very minimum G is equilibrium
DGo and DGT consider only Gibbs free energy of the system if
Gproducts and Greactants mixing is considered.
Equilibrium
G is at a minimum
Goreactants Goreactants
Gibbs Free Energy, G
Gibbs Free Energy, G

ΔGo
ΔGo = Goproducts-Goreactants <0
G of system w/ mixing
Goproducts
Goproducts
Pure Pure AA AB BB BB BB
Reactants Progress of Reaction Products AA
AA AA BA BB
A B Pure Pure
Reactants Progress of Reaction Products
A B
A reaction with DGo <0 does not go to completion but
makes more products than reactants; the more
negative DGo, the more products that are made
n-butane ® isobutane DGo = -2.26 kJ
At equilibrium
Xn = 0.228 Xiso = 0.771
Lower, S. The road is downhill: Free energy and equilibrium. Thermodynamics of Chemical Equilibrium. 2007.
Simon Fraser University. 2 Dec 2009 <http://www.chem1.com/acad/webtext/thermeq/TE5.html>.
A reaction with DGo > 0 will form some product; the more
positive DGo, the smaller the quantity of products made.
N2O4 Û 2NO2 DGo = (103.6-98.3) = +5.3 kJ
Gibbs free energy (G) if no mixing

(DGo)
G with mixing
equilibrium
Lower, S. The road is downhill: Free energy and equilibrium. Thermodynamics of Chemical
Equilibrium. 2007. Simon Fraser University. 2 Dec 2009
<http://www.chem1.com/acad/webtext/thermeq/TE5.html>.
2) K: the equilibrium ratio
Law of mass action

At equilibrium (the minimum Gibbs free energy
of a reaction), the composition of the
reaction mixture can be expressed in terms
of an equilibrium constant (K)
a A(g) + b B(g) Û c C(g) + d D(g)

(aC ) c (aD ) d
K=
(aA ) a (aB ) b
a is an activity
Writing Equilibrium Constants
Po = 1 bar
Activities aJ are used: unitless
co = 1 M
[ ] (concentration)
mol solute
M=
L solution
Activities account for deviations from ideality and
for intermolecular forces
Simplified form can be used for low P and dilute solutions

Solute: a dissolved substance
Solvent: the most abundant component
of a solution; the compound of a
solution in which the other components
are considered to be dissolved
Solution: A homogeneous mixture
[ ] (concentration)
mol solute
M(olarity) =
L solution
http://introtochem.wordpress.com/modules/module-10-part-1/
a A(g) + b B(g) Û c C(g) + d D(g)
(PC / P o )c (PD / P o )d
K=
(PA / P o )a (PB / P o )b
Unitless
(PC )c (PD )d
simplified : K =
(PA )a (PB )b
K = KP use equilibrium pressures (bar) for gases
Kc an equilibrium constant calculated using

equilibrium concentrations in M (mol/L) instead of
pressures for gases
Note: Aqueous solutions are always included in M; they do not
differ for Kp or Kc
1) 2 NO(g) + Cl2(g) ↔ 2 NOCl(g)
(PNOCl ) 2 [NOCl]2
K= Kc =
(PNO ) 2 (PCl2 ) [NO]2 [Cl2 ]
2) H2O(l) ↔ H2O(g)
€
K = PH 2O (g ) K c = [H 2O(g ) ]
3) AgCl(s) ↔ Ag+(aq) + Cl-(aq)

€
K = [Ag+][Cl-]
K is a constant
There may be different quantities of reactants and products
in the equilibrium mixture, but the same K.
(PSO3 )2
2 SO2(g) + O2(g) ßà 2 SO3(g) K =
(PSO2 )2 PO2
(0.0840)2
K= = 0.0415
Equilibrium pressures 2
(0.660) (0.390)
PSO2(bar) PO2(bar) PSO3(bar) Total P (bar) K
0.660 0.390 0.0840 1.1340
0.0380 0.220 0.00360 0.2616 0.0408
0.950 0.880 0.180 2.0100 0.0408
1.44 1.98 0.410 3.8300 0.0409
Average K = 0.0410
3) K and Kc
Cl2(g) + Ni(s) ↔ 2Cl- (aq) + Ni2+(aq)
[Cl − ]2 [Ni 2+ ]
Kc = n
[Cl2 ] P = (RT)
V
[Cl − ]2 [Ni 2+ ] [Cl − ]2 [Ni 2+ ]
K= =
PCl2 [Cl2 ](RT)
€
1
= Kc
RT
−1
= ( RT ) K c
Δn = ngas products − ngas reactants
" c o RT % Δn
K= $ o ' * (Kc) If Dn = 0, then K = Kc
# P &
N2(g) + 3 H2(g) Û 2 NH3(g) Kc = 2.4x10-3 @1000 K.
Find K. Dn= 2 - 4 = -2
Δn
" c RT %
o R in L bar
K= $ o ' * (Kc)
# P &
−2
# 1mol # −2 Lbar & &
% % 8.314 x10 ((1000K ) (
L $ Kmol ' ( * 2.4 x10−3
=%
% 1bar (
€ %
$
(
'
K = 3.472 x10-7
€
4) Linking K to DGT o
ΔG = −RT lnK 298K
R = 8.314 J/(K mol) K (not Kc)
How do Go and K relate? T = 298K
Go kJ/mol K€ Description
200 9.1 x10-36 No reaction
Reactant favored
100 3.0 x10-18
50 1.7 x10-9
10 0.018
1 0.67 Reactants and products
0 1 equally favored
Equilibrium
-1 1.5
-10 56
-50 5.8 x108
-100 3.3 x1017
-200 1.1x103 5 Product
Goes favored
to completion
Gproducts
Greactants Gproducts
DGT = 0
DGT > 0
Greactants @ 100oC
@ 50oC
K< 1 K=1
Greactants
DGT < 0
Example: H2O(l) à H2O(g) Gproducts
@ 140oC
K>1
OpenStax College, Chemistry. OpenStax CNX.
http://cnx.org/contents/85abf193-2bd2-4908-8563-90b8a7ac8df6@9.165
DGo is the difference in Gibbs free energy of the products
and reactants @298K
It tells you IF a reaction is thermodynamically favored
(spontaneous) @298K and HOW reactant or product
favored the reaction is @298K
DGo = -RTlnK298 T = 298K
DGT is the difference in Gibbs free energy of the products

and reactants @T
It tells you IF a reaction is thermodynamically favored
(spontaneous) @T and HOW reactant or product favored
the reaction is @T
DGT = -RTlnKT
The more negative the DGT, the greater the K.
The more positive the DGT, the smaller the K.
5) K, DGT and temperature
DGT and K change with T (the target moves)
N2O4 Û 2 NO2 DH > 0

G vs. mol N2O4 Reacted
T (K) DGT (kJ) K 5
273 9.198 0.017 0

0 0.2 0.4 0.6 0.8 1
298 4.803 0.144 -5

G (Gibb free enegy)
273 K
-10
330 -0.8239 1.35 298 K
-15 330 K
373 -8.385 2.703 373 K
-20
400 K
400 -13.132 51.87 -25
-30
ΔGT = −RT lnKT -35

Quantitative changes in K with T
o o
ΔG T = −RT lnKT = ΔH − TΔS
−( ΔH o − TΔSo ) −ΔH o ΔSo

lnK = = +
RT RT1 R
$ −ΔH o ΔS o ' $ −ΔH o ΔSo '

lnK1 − lnK 2 = & + ) − & + )
% RT1 R ( % RT2 R (
van’t Hoff equation Multiply both sides by -1,

o combine and rearrange
K 2 ΔH $ 1 1 '
rxn
ln = & − )
K1 R % T1 T 2(
Note: For reactions involving gases, use K (not Kc)
2NO(g) ↔ N2(g) + O2(g) K298 = 2.2 x1030 Find K @ 273K
DHorxn = -180.5 kJ; DSorxn = -24.77 J/K; DGorxn = -173.1 kJ
Method 1: DGT = -RTlnKT
ΔGT = −RT lnKT Make sure to use J for all units
ΔG273 = −R(273K)lnK 273 = ΔH o − 273K * ΔS o

J kJ 1000J J
−8.314 * 273K lnK 273 = −180.5 * − 273K * (−24.77 )
Kmol mol 1kJ Kmol
K 273 = 1.75x10 33
o
K 2 ΔH rxn $1 1'
Method 2: ln = & − )
K1 R % T1 T 2(
€
−180.5kJ 1000J
K 273 * # 1 1 &
ln mol 1kJ
€ 30 = J
% − (
2.2x10 $ 298K 273K '
8.314
Kmol
K 273 = 1.73x10 33
van’t Hoff Graphs
Co(H2O)6+2(aq) + 4Cl-1(aq) <--> CoCl4-2(aq) + 6 H2O(l)
−ΔH o ΔS o
ln K = +
RT R
−ΔH o
= −5594(Kelvin)
R
o # 8.314J &# 1kJ & kJ
ΔH = 5594K % (% ( = 46.5
$ Kmol '$ 1000J ' mol
ΔS o
= 7.505
R
" 8.314J % J
ΔS o = 7.505$ ' = 62.4
# Kmol & Kmol J. Chem. Educ. 2012, 89, 533-535.
6) Q: Where does the “equal” in equilibrium come from?
Equilibria have both a significant forward and reverse

rate of reaction. A Û B Forward reaction: A → B
Reverse reaction: A ¬ B
When equilibrium
is reached, the
rates of the
forward and
reverse reaction
are equal AND are
NOT equal to 0.
The concentrations of reactants and products may be equal

to one another at equilibrium but usually are not!
Equilibrium: Constant Concentrations
N2(g) + 3 H2(g) Û 2 NH3(g) K >1; DGT < 0
-no NET change in concentrations of reactants and

products when the system is at equilibrium
-Must be some of each reactant and product when the

system is at equilibrium
[Online image]. Retrieved September 6, 2016 from
http://wps.prenhall.com/wps/media/objects/3312/339
1885/blb1502.html
7) K and Q N2(g) + 3 H2(g) Û 2 NH3(g)
Simplified QC:
Apply the Law of Mass action at
2
any point during the reaction [NH 3 ]
and get Q: the reaction quotient
Qc = 3
[N 2 ][H 2 ]
aA+ b B Û c C+ d D
c d Q<K
(aC ) (aD )
Q= a b €
(aA ) (aB )
K is a specific example of Q
equilibrium Q = K
at equilibrium Q = K
Qc = Kc
Q tells you the direction to K
Q<K
Q=K
Q>K
Q<K Q=K Q>K

Reaction forms @ equilibrium Reaction forms
more products more reactants
[Online image]. Retrieved October 2 from:

http://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Equilibria/Chemical_Equilibria/The_Equilibrium_Consta
nt/Calculating_An_Equilibrium_Concentration_From_An_Equilibrium_Constant/Writing_Equilibrium_Constant_Expressions_
Involving_Gases/Gas_Equilibrium_Constants%3A_Kc_And_Kp
8) DGto equilibrium
DGto eq is the difference in Gibbs energy between where the
reaction is and G @ equilibrium (the minimum G of the
system) DG = 0
eq
The sign of DGto eq tells

you the direction to
equilibrium
DGto eq@B = GB – Geq > 0
DGto eq = Gright - Gleft
GA
_
DGto eq @ A = Geq- GA < 0
Geq GB _
DGto eq changes as the concentrations of reactants and

products change (just like Q)
DGto equilibrium
o
ΔGtoeq = ΔG +RT lnQ
sub DGo = -RTln K
DGto eq = -RTln K + RTlnQ
combine terms:
DGto eq = RTln(Q/K) Q<K
Reaction forms
Q=K
@ equilibrium
Q>K
Reaction forms
Q<K Q>K
DGto eq <0. Q=K DGto eq >0.
DGto eq = 0
Forward rxn @ equilibrium Reverse rxn
spontaneous spontaneous
DGT and K: related to the absolute difference in
Gibbs free energy between products and
reactants
Tell you how far towards the products the
reaction will go.
Have a single value at each T
DGtoeq and Q: For any point along the reaction

(can have many different values)
Tells you if the reaction will make more products
or reactants from that point
9) K, Q, and ICE ICE 1
PCl5(g) Û PCl3(g) + Cl2(g)
At a certain temperature, the initial concentrations are PCl5(g)
(1.0 M), PCl3(g) (0.5M), and Cl2 (0.5M). At equilibrium the
concentration of Cl2 is 0.243 M. Calculate the value of Kc.
Use moles, ↔
molarity or PCl5(g) PCl3(g) Cl2(g)
pressure Initial
Stoichiometric
coefficients Change
and sign
Equilibrium
Sum down the
columns; go
into K or Kc
ICE 1 PCl5(g) Û PCl3(g) + Cl2(g)
At a certain temperature, the initial concentrations are PCl5(g)
(1.0 M), PCl3(g) (0.5M), and Cl2 (0.5M). At equilibrium the
concentration of Cl2 is 0.243 M. Calculate the value of Kc.
PCl5(g) ↔ PCl3(g) Cl2(g)

Initial 1.0M 0.5 0.5
Change +x -x -x
0.5-x = 0.243
Equilibrium 1+x 0.5-x 0.243 0.257 = x
1.257 0.243
[PCl3 ][Cl2 ]
Kc =
[PCl5 ]
0.243* 0.243
= = 0.053
1.257
ICE 2: Use Q and K to Determine
Equilibrium Concentrations
H2 (g) + I2 (g) ↔ 2 HI(g) K = 25
If hydrogen gas (PH2 = 1 bar) is mixed with iodine (PI2 =

1bar) gas and HI(g) at a partial pressure of 2 bar, what
are the equilibrium pressures of the gases?
K = 25
H2(g) I2(g) ↔ 2 HI(g)
2 bar
Initial 1 bar 1 bar
-x -x +2x
Change
Equilibrium 1-x 1-x 2+2x
4 4 20
bar bar bar
7 7 7
2
Q=
(P )
HI
=
(2)2
=4 (P )HI
2
(PH 2 )(PI 2 ) (1)(1) K=

(PH 2 )(PI 2 )
Q < K shift towards products (2 + 2x )
2
25 =
(1− x)(1− x)
2 + 2x
5=
1− x
5 − 5x = 2 + 2x
3
=x
7
ICE 3: Adding to a system at equilibrium
2
H2 (g) + I2 (g) ↔ 2 HI(g) K = 25 K=

(P )
HI
(PH 2 )(PI 2 )
The system is at equilibrium when the partial pressures of H2 and I2 are
each 4 bar and the partial pressure of HI is 20 bar. HI is added, doubling
the partial pressure. What are the new equilibrium pressures?
↔
H2(g) I2(g) 2 HI(g)
Initial
Change
Equilibrium
ICE 3: Adding to a system at equilibrium
2
H2 (g) + I2 (g) ↔ 2 HI(g) K = 25 K=

(P )
HI
(PH 2 )(PI 2 )
The system is at equilibrium when the partial pressures of H2 and I2 are
each 4 bar and the partial pressure of HI is 20 bar. HI is added, doubling
the partial pressure. What are the new equilibrium pressures?
↔
H2(g) I2(g) 2 HI(g)
Initial 4 4 40
Change +x +x -2x
Equilibrium 4+x 4+x 40-2x
2
25 =
( 40 − 2x ) 48
}
(4 + x)(4 + x) PH 2 = PI 2 =
7
K = 25
40 − 2x 20 240
5= x= PHI =
4+ x 7 7
10) Equilibrium response to stressors:
a) Adding a reactant or product Q=
[H ][CH COO ] +
3
−
[CH 3 COOH]
Just before t 1 CH3COOH(aq) Û H+(aq) + CH3COO-(aq)

initial equilibrium
Q=K
@ t1
CH3COOH added
Q<K
@ t2
New equilibrium
K is same value even t1 t2
though concentrations
are different at each [Online image] Retrieved October 2, 2016 from https://oscss-
chemistry.wikispaces.com/Calculating+for+Equilibrium+C(K)o
“new” equilibrium nstant
Demo: Adding a reactant or product
[Co(H2O)6 +2 ][Cl − ]4
CoCl42-(aq) + 6H2O(l) Û Co(H2O)62+(aq) + 4Cl-(aq) Q=
[CoCl 4 −2 ]
Method 1: LeChâtelier's Principle

If a system at equilibrium is stressed, it will respond so as
to oppose or undo the stress.
*Note: adding or taking away solids and pure liquids will

have no effect on equilibrium (the are not in the Q
expression) unless they are the solvent (H2O) or unless
they are completely removed.
Method 2: Equilibrium Law (Q)

The system will proceed to bring Q and K equal
to each other.
Q<K Q=K Q>K
*Not effective for evaluating temperature effects. Reaction forms @ equilibrium Reaction forms
b) Changing Temperature
LeChâtelier's Principle: If a system at equilibrium is
disturbed or stressed by a change in temperature it will shift
the equilibrium so as to oppose the stress.
2 NO2 (g) ↔ N2O4 (g) ΔH = -24.02 KJ

(red-brown) (colorless) + “heat”
Warm: Cold:
P N 2O4
dark red-brown colorless K= 2
lower K higher K (PNO2 )
For an exothermic reaction (ΔHº < 0):
– Temperature increases favor the reactants (K becomes smaller)

€ favor the products (K becomes larger)
– Temperature decreases
Stress: Change T
Response: Change K
“heat” + I2(s) Û I2(g) DH > 0
K = PI 2( g)
Cold: Warm:
more solid more gas
bulb lighter darker purple
€
lower K higher K
For an endothermic reaction (ΔHº > 0):

–Temperature increases favor the products (K becomes larger)
–Temperature decreases favor the reactants (K becomes smaller)
For enthalpically neutral reactions (ΔHº = 0):
Temperature has no effect
c) Changing volume
What happens I2(g) Û 2 I(g) Q =

PI 2
if the volume PI 2
decreases? " nI %2
$ '
#V& (n I ) 2
Qc = = V¯ Q>K shift ¬
" n I2 % n I *V
2€
$ '
#V &
LeChatelier: Compression results in an increase in

pressure; equilibrium will shift to the side with fewer moles
(of gas) €
to minimize the increase in pressure
* For aqueous ions water is volume

CoCl42-(aq) + 6H2O(l) Û Co(H2O)62+(aq) + 4Cl-(aq)
Stress: Change Volume (aqueous)
CoCl42-(aq) + 6H2O(l) Û Co(H2O)62+(aq) + 4Cl-(aq)
[Co(H2O)6 +2 ][Cl − ]4
Q=
What is the effect of adding water? [CoCl4 −2 ]
4
⎡ nCo(H2O)6 +2 ⎤ ⎡ nCl − ⎤
⎢ ⎥⎢ ⎥
Start at equilibrium: Q = K Q=
⎢⎣ V ⎥⎦ ⎣ V ⎦
⎡ nCoCl4 −2 ⎤
⎢ ⎥
⎢⎣ V ⎥⎦
Add water: immediately
(nCo(H2O)6 +2 )(Cl − )4
V↑Q↓ Q<K Q=
(
nCoCl4 −2 V 4 )
Response: goto products until back to

equilibrium Q = K
Inert Gas added at constant P
vs. constant V
2
! nNH 3 $
# & 2 2
" V % nNH
V3
3 H2(g) + N2(g) ⇌ 2 NH3(g)
Qc = 3
=
! nH 2 $ ! nN2 $ nH3n2 N2
# & # &
" V % "V %
Add Xe(g) to a rigid container at constant T
A non-reactive gas has no effect on the partial pressures of
reaction gases in a rigid container; so no response to this
stress
Add Xe(g) to a flexible container at constant T

Adding a non-reactive gas to a flexible container increases the
container volume resulting in a shift to the side with more moles of
gas
10 d) Catalyst and Stress summary
Adding a catalyst changes how reactants form
products and thus how fast the reaction takes
place, but does not affect K.
http://www.columbia.edu/cu/biology/courses/c2005/lectures/lec6_09.html
Type of Stress Response
Add/remove gas/aqueous Evaluate w/ LeChat or Q
product or reactant
Add or remove pure solid or None *unless H2O(l) and
liquid aqueous solutes are present or
all removed
Change temperature Need sign of DH to evaluate w/
LeChat ***K changes****
Volume change for gases Evaluate w/ Qc or LeChat (ie, if
H2O(l)= volume of aqueous ions pressure decrease shift to more
moles of gas; if water added
shift to more moles aq ions)
Catalyst None
Add inert gas (constant volume) None
Add inert gas (constant P) Increases V, see above

11) Disturbance graph
CO(g) + Cl2(g) Û COCl2(g) DH < 0
http://www.coolschool.ca/lor/CH12/unit2/U02L05.htm
Immediate changes with stressors:
1) add/remove and 2) volume
Q K
Reactants à Products Q<K

DGtoeq <0
3
EQ Q>K
Q =K
2
1
DG(toeq) DGtoeq= 0 DGtoeq > 0
0
-1
-2
-3
-4
-5
-6
-7
Immediate changes with stressors: 3) Temperature
DGT and K change with T (the target moves)
Where the system is (Q) does not immediately change.
What happens to DGtoeq?
N2O4 Û 2 NO2 DH > 0

G vs. mol N2O4 Reacted
T (K) DGT (kJ) K 5
273 9.198 0.017 0

0 0.2 0.4 0.6 0.8 1
298 4.803 0.144 -5

G (Gibb free enegy)
273 K
-10
330 -0.8239 1.35 298 K
-15 330 K
373 -8.385 2.703 373 K
-20
400 K
400 -13.132 51.87 -25
-30
ΔGT = −RT lnKT -35

What changes immediately?
DG T K DGtoeq Q
Add/ NC NC If now goto products then DGtoeq
remove goes from 0 à negative and go Q=K to
(gas or aq) Q<K
Volume NC NC
If now goto reactants, then DGtoeq
goes from 0 à positive and go Q=K to
Q>K
Temp Depends +DH, T If now goto products NC
on sign of up, K then goes from 0 à
DS larger negative
Use DG=
DH – T*DS -DH, T If now goto reactants,
to evaluate up, K then goes from 0 à
smaller positive
When does a response undo a stress?
NEVER when there is a temperature change.
For a system with a single component in the equilibrium

expression, it will be restored after an 1) add/remove or 2)
volume stress
CaSO4 !2H2O(s) ßà CaSO4 !1/2H2O(s) + 3/2 H2O(g)

When does a response undo a stress?
3) For a system with All of the components that go into the

equilibrium expression on the same side of the equilibrium
and in the same phase, a volume stress will be undone.
NH3(g) + HCl(g) ßà NH4Cl(s)
PbCl2(s) ßà Pb+2(aq) + 2 Cl-(aq)

12) K* and Hess’ Law
Multiply equation, raise K to that power
1) N2(g) + 3 H2(g) Û 2 NH3(g) Kc1 = 3.5x108
[NH 3 ]2
K c1 = 3
[N 2 ][H 2 ]
2) 1/2 N2(g) + 3/2 H2(g) Û NH3(g) Kc2 = ?
[NH 3 ] 1/ 2 8 1/ 2 4
Kc2 = 1/ 2 3/2
= K c1 = (3.5x10 ) = 1.87x10
[N 2 ] [H 2 ]
*different rules for K than for DH, DS, DG
Hess’s Law and K
Add equations, multiply Ks
PC
A(g) + B(g) Û C(g) K1 = 10 =
PA PB
C(g) Û D(g) + E(g) PD PE
K 2 = 0.08 =
PC
€
A(g) + B(g) Û D(g) + E(g)
€ PD PE PC PD PE = K * K
K3 = = * 1 2
PA PB PA PB PC
K 3 = 10 * 0.08 = 0.8
€
Hess’s Law and K:
When you reverse an equation, invert its
equilibrium constant.
1) N2(g) + 3 H2(g) Û 2 NH3(g) Kc1 = 3.5x108
2) 2 NH3(g) Û N2(g) + 3 H2(g) Kc2 = 1/3.5x108

OR (3.5x108)-
1
Topic 6 Solutions
1) Salts in water (solid in liquid)
a)DHsol, DHlat DHhyd
b) Ksp
i. Soluble vs. insoluble
ii. How much dissolves?
iii. Common ion effect
iv. When do I get a precipitate?
2) Gas in liquid
3) Solution Accounting
Ionic Bond
Electrons are completely transferred; no sharing
Salts
Cation: metal ion or ammonium
(ie, Mg+2, Cu+1 NH4+)
Anion: Oxide, sulfide, halide, or polyatomic

ion
(ie, O-2, Cl-, NO3-, PO43-)
1) Salts Dissolving and Dissociating in Water
NaCl(s) à Na+(aq) + Cl- (aq) DHo = DHosol

• Salt dissolves (mixes with water)
NaCl(s) à NaCl(aq)
make IMF with water
• Salt ions dissociate
NaCl(aq) à Na+(aq) + Cl –(aq)
break ionic bond make ion IMF with water
• Water is not “included” in the balanced equation
Assume a dilute solution so that the result of dissolving is only solute-solvent

interactions
Animation of NaCl dissolving in water

http://www.chem.iastate.edu/group/Greenbowe/sections/projectfolder/flashfiles/thermochem/s
olutionSalt.html
Salts in water: Dissolving equilibrium
Na(CH3CO2)(s) <--> Na+1(aq) + CH3CO2-1(aq) Ksp = [Na+1][CH3C
G reaches a minimum @saturation (equilibrium) point
DGtoeq < 0 (Qsp<Ksp) dissolving

CaSO4(s) ® Ca2+(aq) + SO42-(aq)
Gibbs free energy ---->
Supersaturation =
past equilibrium
DGto eq = 0 equilibrium point;
saturation saturation Qsp = Ksp
CaSO4(s) Û Ca2+(aq) + SO42-(aq)
dissolving precipitation
DGtoeq> 0 (Qsp>Ksp)
Concentration of solute ---->
supersaturated; precipitation
CaSO4(s) ¬ Ca2+(aq) + SO42-(aq)
Lattice enthalpy (solid to gas ions) DHlat > 0 (endothermic)
Enthalpy of hydration (gas to aq) DHhyd < 0 (exothermic)
LiCl(s) ® Li+(g) + Cl-(g) Li+(g) ® Li+(aq)

DHhyd = -499 kJ
DHlat= +848 kJ
Cl-(g) ® Cl-(aq)
DHhyd = -381 kJ
DHsol = DHlat + DHhyd

LiCl(s) ® Li+(aq) + Cl- (aq) DHsol(LiCl) = (848 -499-381)kJ= -32 kJ
[Online Image] Retrieved October 4, 2016 from: http://www.4college.co.uk/a/O/energy.php

Lattice Compound DHlat(kJ/mol) Compound DHlat(kJ/mol)
Enthalpies LiCl 848 CaF2 2630
NaF 918 CaCl2 2258
NaCl 780 CaBr2 2176
NaBr 742 KBr 679
NaI 705 NH4Cl 640
International Baccalaureate Organization 2007: Accessed October 6, 2016 From:
http://www.savitapall.com/IB%20Information/notes/Chem%20Data%20Booklet_07-09.pdf
Chem Factsheet No 94 Enthalpies of Solution www.curriculum-press.co.uk Accessed Oct 6, 2016
From:https://www.scribd.com/doc/38582471/Enthalpies-of-Solution
Enthalpies of Ion DHhyd (kJ/mol) Ion DHhyd (kJ/mol)

Hydration of Li+ -499 F- -457
Gaseous Ions Na+ -390 Cl- -381
K+ -305 Br - -351
NH4+ -307 I- -307
Ca+2 -1562 NO3- -314
D.W. Smith, J. Chem. Educ., 54, 540 (1977).
+ DHsol - DHsol
Salt DHsol (kJ/mol) Salt DHsol (kJ/mol)

NaCl 3.88 LiCl -37
NaNO3 20.5 LiOH -23.6
NH4Cl 14.6 CaCl2 -82.9
NH4NO3 25.7 Ca(OH)2 -16.2
[Online Image] Retrieved October 4, 2016 from: http://www.4college.co.uk/a/O/energy.php

Parker, V.B., Thermal Properties of Uni-Univalent Electrolytes, Natl. Stand. Ref. Data Series-Natl .Bur. Stand.(U.S.), No. 2,
1965. Accessed October 6, 2016 from:
http://sites.chem.colostate.edu/diverdi/all_courses/CRC%20reference%20data/enthalpies%20of%20solution%20of%20electrol
ytes.pdf
Problem 1
What is the final temperature when 7.2 g CaCl2
(MW = 111, DHsol = -81.3 kJ/mol ) are dissolved in
500 mL of water (1g/mL) at 25oC?
Assumptions:
Mass of solution = mass water
Cs solution = Cs water = 4.184 J/(g oC)
Problem 1
What is the final temperature when 7.2 g CaCl2
(MW = 111, DHsol = -81.3 kJ/mol ) are dissolved in
500 mL of water (1g/mL) at 25oC?
CaCl2(s) ® Ca2+(aq) + 2 Cl-(aq) DH = -81.3 kJ
qrxn = −qwater
−81.3kJ # 7.2g &# 1mol &
% (% ( = −mCsΔT
mol $ '$ 111g '
#1000J & 4.184J
−5.27kJ% ( = −500g o (Tf − 25) oC
$ 1kJ ' gC
2.52 = Tf − 25
Assumptions:
27.52 = Tf Mass of solution = mass water
Cs solution = Cs water
= 4.184 J/(g oC)
Soluble Compounds
dissolve completely (one way)
assume that what dissolves dissociates
(K “large” so equilibrium not considered)
(memorize)
1) Group 1 and NH4+ salts are “completely”

soluble NaHSO à Na+ + HSO -1
3(s) (aq) 3 (aq)
2) All nitrates are “completely” soluble

Al(NO3)3(s) à Al+3(aq) + 3 NO3-1(aq)
Insoluble compounds are in equilibrium

Solubility Rules (not to be memorized)
1. All compounds of Group IA elements are soluble.
2. All ammonium salts (NH4+) are soluble.
3. All nitrate (NO3-), chlorate (ClO3-), perchlorate (ClO4-),
and acetate (CH3COO-) salts are soluble.
4. All chloride (Cl-), bromide (Br-), and iodide (I-) salts are
soluble except for those of Ag+, Pb2+, and Hg22+.
5. All sulfate (SO42-) compounds are soluble except those
of Ba2+, Sr2+, Ca2+, Pb2+, Hg22+, and Hg2+
6. All hydroxide (OH-) compounds are insoluble except
those of Group I-A and Ba2+, Ca2+, and Sr2+
7. All sulfide (S2-) compounds are insoluble except those
of Groups I-A and II-A
8. All sulfites (SO32-), carbonates (CO32-), chromates
(CrO42-), and phosphates (PO43-) are insoluble
For reference (NOT memorization) http://en.wikipedia.org/wiki/Solubility_chart
How much insoluble salt dissolves in water?
(use ICE table)
dissolve
AgCl(s) ⇌ Ag+(aq) + Cl-(aq) Ksp = [Ag+][Cl-] = 1x10-10

precipitate Ksp an equilibrium constant
for the process of dissolving
I 0 0 an ionic salt in water
C +s +s
E s s Ksp = [Ag+][Cl-] = s2 = 1x10-10
s = 1 x10-5
The solubility (s) of AgCl is 1x10-5 M
The molar solubility of a salt (s) is the number of moles that
can dissolve per L of water.
Saturated: at equilibrium
Comparing Solubilities
Which has a higher solubility?
CaCO3 Ksp = 1x10-11 3.16x10-6 = s
CaF2 Ksp = 1x10-12 6.39x10-5 = s
CaF2(s) Û Ca+2(aq) + 2F-(aq) Ksp = 1x10-12

= [Ca+2][F-]2
I 0 0 = (s)(2s)2
C +s +2s = 4s3
E s 2s 6.39x10-5 = s
Common Ions: How much salt dissolves?
(Use ICE table)
What is the solubility of CaF2 in a 0.1 M NaF solution?
CaF2 Ksp = 1x10-12
CaF2(s) Û Ca+2(aq) + 2F-(aq) Ksp = [Ca+2][F-]2
I 0 0.1
1x10-12 = s(0.1+2s)2
C +s +2s
E s 0.1 + 2s 1x10-10 = s
6.39x10-5 = solubility
in pure water
Common ion effect: the decrease in solubility of an ionic
salt caused by the presence in solution of another solute
that contains one of the same ions as the salt.
What is the solubility of MgNH4PO4(s) Ksp = 2.5x10-13 in
0.1M (NH4)3PO4?
soluble
(NH4)3PO4(s) à 3 NH4+(aq) + PO4-3(aq)
0.1mol(NH 4 )3 PO4 ! 3molsNH 4+ $ 0.3molNH 4+
# &=
L " 1mol(NH )
4 3 PO4% L
0.1mol(NH 4 )3 PO4 " 1molsPO4−3 % 0.1molPO4−3

$ '=
L # 1mol(NH 4 )3 PO4 & L
MgNH4PO4(s) ßà Mg+2(aq) + NH4+(aq) + PO4-3(aq)

I 0 0.3 0.1
C +x +x +x
E x 0.3+x 0.1+x
Ksp=[Mg+2][NH4+][PO4-3] = (x)(0.3+x)(0.1+x) (shortcut)
2.5x10-13 = (x)(0.3)(0.1)
8.33x10-12 = x
Do I get a precipitate?
( Yes or no: compare Q to K)
If 10 mL of 0.001 M Na2CO3 and 10mL of

0.025M AgNO3 are mixed together, does
Ag2CO3 (Ksp =6.2x10-12) precipitate?
Dilution
50.0 mL of the 0.1M KF was diluted to 100. mL. What
is the new concentration?
H2O
0.005 mol KF 0.005 mol KF
0.1molKF " 1L %
50.0mL $ ' = 0.005molKF
L #1000mL &
0.005molKF "1000mL % molKF

$ ' = 0.05
€ 100mL # 1L & L
M1V1 = mols1 = mols2 = M 2V2

€
Do I get a precipitate?
( Yes or no: compare Q to K)
If 10 mL of 0.001 M Na2CO3 and 10mL of

0.025M AgNO3 are mixed together, does
Ag2CO3 (Ksp =6.2x10-12) precipitate?
2−
Ag2CO3(s) ⇔ 2Ag+(aq) + CO3(aq)
Q = [Ag+ ]2 [CO32− ]
2
# # 0.01L && # # 0.01L &&
= % 0.025M % (( % 0.001M % ((
$ $ 0.02L '' $ $ 0.02L ''
−8
= 7.81x10 > K
Yes
When (@ what concentration)
will I get a precipitate?
(use K expression to compare when ions come from
different sources)
NaF(s) is added to a solution that is 1x10-6M Ca(NO3)2(aq).
At what concentration of F- will a precipitate first appear?
CaF2(s) Û Ca+2(aq) + 2F-(aq) Ksp = 1x10-12 = [Ca+2][F-]2
Ca+2 is set. F- is changing via addition from a source that

is NOT the insoluble salt.
Ksp = 1x10-12 = [Ca+2][F-]2 = (1x10-6 )(x)2
1x10-3= x = [F-] F- comes from external
source so no “2”
When [F-] = 1x10-3M, CaF2 will start to precipitate
Na3PO4 is added to a solution containing
0.1 M Al(NO3)3(aq), and 0.1M Mn(NO3)2(aq).
Which salt AlPO4 (Ksp = 9.8x10-21) or
Mn3(PO4)2 (Ksp = 1x10-22) will precipitate
first?
AlPO4 ßà Al+3 + PO4-3 Mn3(PO4)2 ßà 3Mn+2 + 2PO4-3

Ksp =[Al+3 ][PO4-3] Ksp =[Mn+2 ]3[PO4-3]2
Ksp = 9.8x10-21 = (0.1) [PO4-3] Ksp = 1x10-22 = (0.1)3x2
9.8x10-20 = [PO4-3] x = 3.16x10-10 = [PO4-3]
[PO4-3] starts at 0 and reaches the smallest

concentration first.
How much is left when the second precipitate forms?
Na3PO4 is added to a solution containing 0.1 M Al(NO3)3(aq),
and 0.1M Mn(NO3)2(aq). The AlPO4 precipitates first. What
is the concentration of Al+3 ions left in solution when the
Mn3(PO4)2 begins to precipitate?
Mn3(PO4)2 ßà 3Mn+2 + 2PO4-3
Ksp =[Mn+2 ]3[PO4-3]2
Ksp = 1x10-22 = (0.1)3x2
x = 3.16x10-10 = [PO4-3] AlPO4 ßà Al+3 + PO4-3
Ksp = 9.8x10-21 = [Al+3][PO4-3]
9.8x10-21 = [Al+3][3.16x10-10]
3.1x10-11 = [Al+3]
3.1x10-11/0.1 * 100%
= 0.000000031% left
1) How much solid dissolves or precipitates?
(ICE table) …..changing concentrations of
both ions together.
2) Do I get a precipitate? (compare Q to K)
3) When (at what []) do I get a precipitate?

How much is left when I get a precipitate?
….changing concentration of ions separately
(use K expression)
2) Gas in (or out of) liquid
http://en.wikipedia.org/wiki/Diet_Coke_and_Mentos_eruption#mediaviewer/File:Diet_Coke_Mentos.jpg
Gas Solubility in Liquid
Solubility in water Concept Question 1:
Based on the data in the
graph, an increase in
partial pressure of a
gas leads to an
A. Increase
B. Decrease
in the solubility of the gas.
Figures 10.22 CHEMICAL
PRINCIPLES|ATKINS|JONES|LAVERMAN ©2013 W. H.
FREEMAN AND COMPANY
Henry’s Law
Henry’s Constants kH
in Water at 20oC
Solubility (molarity) of a gas is
directly proportional to its Gas kH (mol/L atm)
partial pressure. Air 7.x10-4
Ar 1.5x10-3
s = kHP CO2 2.3x10-2

He 3.7x10-2
kH Henry’s constant;
H2 8.5x10-4
T dependent Ne 5.0x10-4
N2 7.0x10-4
O2 1.3x10-3
Temperature and Solubility of Gases
Most gases are more soluble in cold water.
Concept Question 2:
What does this tell us
about DHo of dissolving a
gas?
A(g) <-> A(aq)
A) DHo >0
B) DHo = 0
C) DHo < 0
Making IMF
K is greater when T lower
http://webserver.dmt.upm.es/~isidoro/bk3/c07sol/Exercise2.htm
3) Solution Accounting
Concentration Defined
Mole fraction xn = moles n
moles total
molality m = moles solute

kg solvent
Molarity M (c) = moles solute

L solution
% by mass = mass solute*100

total mass
Pick a single quantity to work with.
Accounting The solutions are uniform so every quantity has the
same concentration.
Mole fraction xn = _____moles n_____ pick 100 total moles

moles total (solution)
Molality m = moles solute

pick 1 kg solvent
kg solvent
c Molarity M = moles solute

pick 1 L solution
L solution
** need density to convert out of M or into M
Mass % = ____mass solute____ *100

mass solution (total)
pick 100 g solution
Problem 1
An aqueous solution of H2O2 is 30.0% by mass and has
a density of 1.11 g/mL. Calculate its molarity, molality,
and the mole fraction of H2O2.
An aqueous solution of H2O2 is 30.0% by mass and has
a density of 1.11 g/mL. Calculate its molarity, molality,
and the mole fraction of H2O2.
mass
Density = ....assume 1 L (1000 mL)
V
1.11g
*1000mL = 1110g solution
1mL
mass solute
Use mass % = *100
mass solution
xg H 2O2
*100 = 30% x = 333g H 2O2
1110g total
1mol
333g H 2O2 * = 9.79molH 2O2
34gH 2O2
1molH 2O
1110g total - 333g H 2O 2 = 777g H 2O * = 43.17molH 2O
18gH 2O
Mole fraction xH2O2 = molesH 2O2 = 9.79molH 2O2
= 0.185
moles total 9.79mol + 43.17mol
€
Molality m = molesH 2O2 9.79molesH 2O2 mol
= = 12.6
kgsolvent(H 2O) 0.777kg kg
Molarity
€ M= molesH 2O2 9.79molesH 2O2 mol
= = 9.79
Lsolution 1L L
€
Topic 07: Phase Change /
Colligative Properties/ Liquid-liquid
1) Phase Diagrams
Temperature, Pressure, Triple point
2) Vapor pressure
Clausius-Clapeyron/ van’t Hoff
3) Colligative Properties
a,b) mp lowering, bp elevation, vapor pressure lowering
c) van’t Hoff i
d,e) G vs. T graphs
f) Osmotic pressure
4) Liquid/liquid mixtures
1) Phase Diagrams:
Pressure vs. Temperature
Phase Diagrams:
Effect of Pressure on Boiling Point
How does lowering the external
pressure affect the bp of water?
Lower external pressure
“favors” the gas phase:
less work (-PDV)
required to evaporate;
takes less heat; lower Tb
q needed to evaporate liquid
40
30
20
10
0 [online image]. Retrieved October 9, 2016 from

low P med P high P
http://www.angelfire.com/hi5/phases/diagram.html
break bonds work
Phase Diagrams:
Effect of Pressure on Melting Point
When solid is more dense than liquid
Higher pressure favors more dense (solid) phase
solid ¬® liquid
Positive slope
higher P ¬
Tm increases with pressure

q needed to melt
8
6
4
2
0
low P med P high P
break bonds work

http://2012books.lardbucket.org/books/principles-of-general-chemistry-
v1.0/s15-liquids.html#averill_1.0-ch11_s07_f01 (Accessed Feb 16, 2015)
When solids are less dense
than liquids
Density (g/mL)
gallium - 5.91 (solid) vs 6.095 (liquid)
bismuth - 9.78 (solid) vs 10.05 (liquid)
germanium - 5.323 (solid) vs 5.60 (liquid)
silicon - 2.3290 (solid) vs 2.57 (liquid)
water - 0.917 (solid) vs 0.998 (liquid)
Photo by: Claudio Baldini
ChemEd DL
http://chempaths.chemeddl.org/services/chempaths/?q=book/General%20Chemistry%20Textbook/1
337/further-aspects-covalent-bonding&title=CoreChem:Ice_and_Water
Phase Diagrams:
Effect of Pressure on Melting Point
When liquid is more dense than solid
Higher pressure favors more dense
(liquid) phase
solid ¬® liquid negative slope
Tm decreases with pressure

energy needed for melting
6
2 Rumor: ice “skating” pressure melts

1 solid to form slippery liquid layer
0
low P med P high P [online image]. Retrieved October 9, 2016 from
q work http://www.angelfire.com/hi5/phases/diagram.html
Phase Diagrams: Triple Point
Triple point: 3 phase

boundaries meet on
a phase diagram.
[online image]. Retrieved October 9, 2016 from http://www.angelfire.com/hi5/phases/diagram.html

2) Vapor pressure
Liquid will vaporize until equilibrium is reached. The partial
pressure exerted by the vapor when the vapor and its liquid
(or solid) are in dynamic equilibrium is its vapor pressure.
H2O(l) Û H2O(g) K = PH2O
The more negative DGT, the higher K (vapor pressure).

[online image]. Retrieved October 10, 2016 from: http://www.chemteam.info/GasLaw/VaporPressure.html
Vapor Pressure, IMF, and boiling point
liquid ßà gas
Substance Vapor pressure
@ 25oC in torr
Vapor pressure (K) increases methanol 122.7
with weaker intermolecular ethanol 58.9
forces. water 23.8
benzene 94.6
Vapor pressure (K) increases toluene 29.1
with decreasing boiling point
Methanol is the most
volatile of the liquids in
the table; it has the
highest vapor pressure
Vapor Pressure (K) Changes with T liquid ßà gas +DH
Vapor Pressure of water

Temperature Vapor
oC pressure (torr)
0 4.58
10 9.21
20 17.54
25 23.76
30 31.83
37 47.08
60 149.44
@ bp DGT = 0, K = 1 = Pvap 100 760
Algebra Lab. “Chemistry Graphs Vapor Pressure Curves” [online image]. Retrieved October 10, 2016 from
http://www.algebralab.org/practice/practice.aspx?file=reading_vaporpressurecurves.xml
van’t Hoff Equation
o
K 2 ΔH rxn $1 1'
ln = & − )
K1 R % T1 T 2(
H2O(l) Û H2O(g) K = PH2O
€ Clausius-Clapeyron Equation
P 2, vap ΔHvap, m $ 1 1 '
ln = & − )
P1, vap R % T1 T 2 (
Pressures in same units
DH in kJ/mol
R in J/(K mol) Convert to kJ or J
T in K
€
3) Colligative Properties
"Colligative" comes from the observation that, in
general, the property is influenced only by how
much solute is dissolved in the solvent and not
by the nature of the solute
Entropy increases with solute dissolving in solvent

and creates the following effects:
Vapor pressure lowering P = xsolventPpure
Freezing point depression DTf = i kf *m
Boiling point elevation DTb = i kb *m
Osmotic pressure P = i RTc
Freezing/melting point depression
Dissolving a solute in a pure

liquid (solvent) will increase
the entropy (S) of the system
as it forms a solution.
The increased entropy of

the solution, lowers the
solid ßàliquid Solid ßà solution energy needed to have an
equal number of accessible
energy levels in both solid
and liquid and thus the
melting point.
Lower, S. (2010). Chem 1 Virtual Textbook. Retrieved Oct 4, 2010 from
http://www.chem1.com/acad/webtext/thermeq/TE6.html.
Boiling point elevation/ vapor
pressure lowering
The increased entropy of
the system raises the
energy needed for both
liquid and gas to have an
equal number of
accessible energy levels
and thus equal
possibilities for spreading
out thermal energy and
the equilibrium
liquid ßà gas solution ßà gas
temperature (aka the
boiling point.)

Find the freezing point and boiling point of a
4.03 m sucrose(aq) solution.
Kkg 4.03mol
ΔTf = 1.86 * = 7.49K = 7.49 oC
mol kg
DTf = kf *m Tf = 0 − 7.49 oC = −7.49 oC
DTb = kb *m ΔTb = 0.51

Kkg 4.03mol
* = 2.05K = 2.05 oC
mol kg
€
Tb = 100 + 2.05 oC = 102.05 oC
Solvent mp (oC) kf(K kg/mol) bp (oC) kb(K kg/mol)

acetone -95.4 2.40 56.2 1.71
€ benzene 5.5 5.12 80.1 2.53
cyclohexane 6.5 20.1 80.7 2.79
water 0 1.86 100.0 0.51
Vapor-Pressure Lowering
Raoult’s Law for ideal solutions
Pvap = XsolventPvap,pure
mol(solvent )
X solvent =
mol(solvent ) + mol(all solute particles)
Solutions are most ideal at low solute concentrations

< 0.1 M nonelectrolyte (molecular solutes)
< 0.01 M electrolyte (ionic solutes)
OpenStax College, Chemistry [online image]. Retrieved October 10, 2016. From
http://philschatz.com/chemistry-book/contents/m51088.html
Accounting for ALL particles
dissolved in solution
Molecular solutes (ie polymer, sugar, gas)
Dissolve to yield only one particle
Ionic solute (salts)
Dissociate into multiple ions when dissolving
NaCl(s) ®Na1+(aq) + Cl1-(aq)
Creates 2 moles of ions for every one mole of
salt that dissolves
0.544 mol NaCl makes 1.088 moles solute
particles
Ionic solutes and the van’t Hoff “i” factor
i is the ratio of dissolved particles to dissolved solute. (it converts the
molality of the dissolved solute to the molality of dissolved particles)
What is the freezing point of 0.544 m NaCl(aq)?

When salts dissolve, i = # ions formed; for
NaCl, i = 2 mol ions/1mol NaCl
DTf = ikf *m
m is considered the moles solute NaCl(s)
that dissolves per kg H2O ….a description
of how to prepare the solution
2mol ions 0.544mol solute
ΔTf = kf
1mol solute kg solvent
K kg mol
ΔTf = 2*1.86 0.544
mol kg
ΔTf = 2.023K
Tf = 0 − 2.032 oC = -2.032 oC
“i” and X What is XH2O for 0.5 m Ca(NO3)2?
molsolvent
X solvent =
molsolvent + molsolute particles
€
“i” and X What is XH2O for 0.5 m Ca(NO3)2?
molsolvent
X solvent =
molsolvent + molsolute particles
0.5molCa(NO3 )2
0.5m Ca(NO3 )2 = Pick 1 kg solvent
kg H 2O
! 3 moles particles $
0.5molCa(NO3 )2 # & = 1.5molparticles
" 1mol Ca(NO3 )2 %
! 1000g $! 1mol $
1kgH 2O # &# & = 55.5molH 2O
" 1kg %" 18g %
55.6mol H 2O
X H 2O = = 0.975
55.5mol H 2O +1.5molparticles
Go vs. T for liquid and solution
Go = -TSo + Ho
y = mx + b
Slope change of
solution often shown
as a lower parallel
slope

G vs. T graphs
Real: Ions in Water
DS + =
When ions dissolve in

There is an water, water forms an
increase in ordered shell around the The net effect is
entropy when a ion. The water a smaller
solid dissolves becomes more ordered increase in
in a solvent. (its entropy goes down.)
entropy of the
The magnitude of the solution and thus
effect is very small for a smaller
polar solutes, small for decrease in the
±1 ions, moderate for ±2 freezing point,
ions, large for ±3 ions etc.
Real vs Ideal
G vs.T Plot
for melting point
Concept Question 8
Which will have the higher boiling point (assuming non-ideal
behavior)?
a 2 molal aqueous solution of A, a solute that dissolves to form
a +1 and a -1 ion
OR
a 1 molal aqueous solution of B, a solute that dissolves to form
a +3 ion and three -1 ions.
A. 2 molal solution of A
B. 1 molal solution of B
C. They are the same
D. There is insufficient information to say
A. 2 molal solution of A…same i*m factor; +3 ion in B
interacts with water to lower entropy gained
bp pure liquid
bp solution A
bp solution B
Solution with highly charged ions
[online image]. Retrieved October 11, 2016 from

http://www1.lsbu.ac.uk/water/colligative_properties.html
Semipermeable Membrane
©2010, 2008, 2005, 2002 by P. W. Atkins and L. L. Jones

Osmotic pressure
Osmosis: The flow of a solvent through a (semipermeable)
membrane into a more concentrated solution.
Osmotic pressure (P) : Pressure needed to stop the flow.
Hydrostatic pressure: Pressure created by the difference in
height of the columns after flow = P
Osmoti
c
pressur
e
hydrostatic
P = i RTc = gdh
c concentration
http://chemwiki.ucdavis.edu/Wikitexts/UC_Davis/UCD_Chem_2B/UCD_Chem_2B%3A_Larsen/Unit_II
%3A_States_of_Matter/Solutions/13.5%3A_Colligative_Properties_of_Solutions
M
R in Latm/Kmol
Osmosis vs. Diffusion
http://what-when-how.com/nursing/fluid-and-electrolyte-balance-structure-and-function-nursing-part-2/
The thermodynamics of osmotic pressure
PéVêSê
Osmotic equilibrium, like any kind of equilibrium, occurs

when the free energies (that is, the escaping tendencies) of
the diffusible molecules are the same on the two sides of the
membrane.
Osmosis in the real world
http://chemwiki.ucdavis.edu/Wikitexts/UC_Davis/UCD_Chem_2B/UCD_Chem_2B%3A_Larsen/Un
it_II%3A_States_of_Matter/Solutions/13.5%3A_Colligative_Properties_of_Solutions
Preserving (kill bacteria by lysing with excess sugar or

salt)
Trees evaporate water at leaves, draw water from roots

with osmosis
Measure MW, especially of large molecules like

Reverse osmosis
http://www.water-treatment.com.cn/technologies/RO_Reverse-Osmosis/introduction.htm
4) Ideal Liquid:Liquid Mixtures
Hex Xhex(g) = 6/7 = 0.86

Oct Hex
Hex Xoct(g) = 1/7 = 0.14
Hex Hex
Hex
Oct
Oct Oct
Hex Hex Hex
HexOctHexOct
HexOct Oct Oct Oct Xhex(l) = 10/20 = 0.5
Oct Hex Hex Hex Hex Xoct(l) = 10/20 = 0.5
Oct
Raoult’s Law
Hexane Octane
Pvap,solution = Pvap,hex from solution + Pvap,oct form solution
= Xhex, liquidPvap,pure hex + Xoct, liquidPvap pure oct
[online image]. Retrieved October 11, 2016. from: http://jcsu.jesus.cam.ac.uk/~rpc25/notes/chemistry/phase_equillibria/
Azeotropes Lower solute-solvent IMF DHmix> 0
Example: benzene/ethanol
Non-ideal liquid/liquid
solutions…do not obey
Raoult’s Law
Break AA Make weaker actual
& BB IMF AB IMF
+ DH - DH ideal
Net + DHmix
Lower bp
Higher Pvap
than Raoult
More favorable intermolecular interactions within pure solvent so
molecules inclined to escape to vapor phase
Azeotropes Higher solute-solvent IMF DHmix< 0
Example: Acetone/chloroform
Break AA Make stronger

& BB IMF AB IMF
ideal
+ DH - DH
Net -DHmix actual

Higher bp
Lower Pvap
than Raoult
More favorable intermolecular interactions with other liquid than within
pure solvent so molecules inclined stay in liquid phase
Problem 2
Hexane and octane form an ideal solution. The vapor pressure
of pure hexane @ 323K is 0.55 atm. The vapor pressure of pure
octane @ 323K is 0.09 atm. A mixture of hexane and octane
has a vapor pressure of 0.32 atm @ 323K.
a) What is the mole fraction of hexane in the solution?
b) What is the mole fraction of hexane in the vapor?

Liquid:Liquid Mixtures
Ideal solutions
Hex Xhex(g) = 6/7 = 0.86

Oct Hex
Hex Xoct(g) = 1/7 = 0.14
Hex Hex
Hex
Oct
Oct Oct
Hex Hex Hex
HexOctHexOct
HexOct Oct Oct Oct Xhex(l) = 10/20 = 0.5
Oct Hex Hex Hex Hex Xoct(l) = 10/20 = 0.5
Oct
Raoult’s Law
Hexane Octane
Pvap,solution = Pvap,hex from solution + Pvap,oct form solution
= Xhex, liquidPvap,pure hex + Xoct, liquidPvap pure oct
Problem 2

P vaptotal = x hex,liq (0.55atm) + x oct,liq (0.09atm) = 0.32atm
x(0.55)+ (1 − x)(0.09) = 0.32
x = x hex,liq = 0.5
€
Mole Fraction Liquid vs. Vapor
Benzene
Pvap= 95.1 torr
Toluene
Pvap= 28.4 torr
Xbenzene
vapor
XB(g) = 6/8 = 0.75
B
B XT(g) = 2/8 = 0.25
T
B T
B B
B
T
T T
B B
B B T B T
B T
T
T T XB(l) = 10/20 = 0.5
B B
T B B
T XT(l) = 10/20 = 0.5
Xbenzne liquid
Problem 2
Xhex, liquid = 0.5

b) What is the mole fraction of hexane in the vapor?
Phex = X hex ,gas Ptotal
X hex ,liq Pvap,purehex = X hex ,gas Psolution
0.5(0.55atm) = X hex ,gas (0.32atm)
0.86 = X hex ,gas

Topic 08 Acids and Bases
1) Define Bronsted acid/base
2) Strong vs. weak
3) pH/pOH/Kw/What is neutral?
4) pH/pOH of strong acids/bases
5) pH/pOH weak acids/bases
6) Acid strength
7) Identifying acids and bases
8) pH/pOH of a salt
9) pH/pOH of polyprotic acids and bases
10) Diluting acids: pH and i factor
History of Acids and Bases
Egyptians, Greeks, Romans:
– Acids: vinegar
– Alkali
• potash (K2CO3, wood)
• soda (Na2CO3, alkaline water)
• lime (CaO, shells)
Middle Ages
– Acids
• aqua frotis (nitric acid HNO3),
• aqua regia (a nitric-hydrochloric acid mixture HNO3/HCl)
• oil of vitriol (sulfuric acid H2SO4)
Otto Tachenius and Francois Sylvius (1670s)
– reduced all chemical interactions within the living organism to
acid-base reactions
Kauffman, G. B. "The Bronsted-Lowry Acid-Base Concept" J. Chem Ed. 1988, 65, 2831.
Acids and Alkali Theory
Boyle (1661)
– Acids:
• sour taste
• exceptional solvent power
• the ability to color certain blue vegetable dyes red
• a precipitating action on dissolved sulfur
– Alkalies,
• slippery feel
• detergent properties: ability to dissolve oils and sulfur
• counteract acids and destroy their properties
– Neutral
Lemery (1675)
– Acids: sharp spiky atoms
– Alkalies: round particles
Lavoisier
– Oxygen in 1777
– When sulfur or phosphorus was burned in oxygen, the products dissolved in
water to form acids, so he concluded that oxygen was the element common to
all acid materials.
1) Acids and Bases:
Comparing Definitions
Acid Base
Arrhenius provide H+ in water provide OH- in water
Bronsted proton (H+) donor proton (H+) acceptor
Lewis electron pair acceptor electron pair donor
NH3 + H2O Û NH4+ + OH-

base acid conjugate conjugate
acid base
Concept Question 1
Conjugate base is the species left when an acid
donates a proton.
Conjugate acid is the species formed when a base
accepts a proton
What is the role of OH- in the following reaction?

O2-(aq) + H2O(l) ® 2 OH-(aq)
A. The conjugate acid

B. The conjugate base
C. Both
2) Strong and Weak Aqueous Acids
A strong acid dissociates completely (the reaction is shifted all of
the way to its conjugate base and H+).
HCl(aq) → H+(aq) + Cl-(aq)

acid conj. base
A weak acid does not dissociate completely (an equilibrium is
established in water between the acid, its conjugate base, and H+).
HClO2(aq) ↔ H+(aq) + ClO2- (aq)

acid conj base
[H + ][ClO2− ]
Ka = = 1x10 −2
[HClO2 ]
pKa = -log Ka = 2 Like soluble and
insoluble salts!!
Strong (Aqueous) Acid
(dissociates completely)
Weak (Aqueous) Acid

(equilibrium w/ small K)
Û
2) Strong and Weak Aqueous Bases
A strong base dissociates completely (reaction is shifted all of
the way to its conjugate acid and hydroxide).
NaOH(aq) + H2O(l)
Na+(aq) + OH-(aq) + H2O(l) → Na+(aq) + H2O(l) + OH-(aq)
base conj. acid
A weak base does not dissociate completely (an equilibrium is
established in solution between the base, its conjugate acid, and
hydroxide).
(CH3)3N(aq) + H2O(l) ↔ (CH3)3NH+(aq) + OH-(aq)
base conj. acid
[(CH 3 ) 3 NH + ][OH − ]
Kb = = 6.5x10 =5
[(CH 3 ) 3 N]
pKb = -log Kb = 4.19
There are six strongly dissociating acids:
HCl HNO3
HBr HClO4
HI H2SO4* * (2 H+ to donate)
***sometimes HClO3
Strong bases include:

Gp I hydroxides (LiOH, NaOH, etc.)
Gp II hydroxides (Mg(OH)2, Ca(OH)2, etc.) to the
extent that they are soluble.
NH2-, O-2 , R3C-, H-
•Gp II and O2- make 2 equiv OH-;
•conj acid of NH2- is NH3, a weak base
You should commit the strong acids and bases to
memory.
Identifying Aqueous Acids & Bases From organic:
Molecular Acids: [H+ + (anion)] OR carboxylic acids acid

HCl, H2S, HClO3, H3PO4, CH3COOH O
C
R OH
H2S(aq) Û H+(aq) + HS-(aq)
CH3COOH(aq) Û H+(aq) + CH3COO-(aq) R3N+H
Bases: Hydroxides, amines

NaOH, Ca(OH)2, NH3, (CH3)3N
NH3(aq) + H2O(l) Û OH-(aq) + NH4+(aq)
Amphoteric: H2O
Water is Amphoteric:
- it can act as an acid or a base
Amphiprotic: both a proton donor and acceptor
Autoionization: acid/base equilibrium of water
H2O(l) Û H+(aq) + OH-(aq)

Kw = [H+][OH-] = 1x10-14 at 25oC
If [H+] =1x10-2
1x10-14 = [H+][OH-]
= 1x10-2[OH-]
1x10-12 = [OH-]
3) pH/pOH
pH = -logaH+ [OH-]
Simplified:
pH = -log[H+]
pOH = - logaOH- [H+]
Simplified:
pOH = - log[OH-]
Kw = [H+]*[OH-] = 1 x10-14
-log ([H+]*[OH-]) = - log (1 x10-14)
-log [H+] - log[OH-] = 14
pH + pOH = 14 [online image]. Retrieved February 5, 2017 from:
Compoundchem.com/2015/07/09/ph-scale/
What is neutral? (at 25oC)
I 0 0
C +x +x
E x x
Kw = [H+]*[OH-] = 1 x10-14
(x)(x) = 1 x10-14
x = 1x10-7 = [H+] = [OH-]
pH = -log(1x10-7) = 7
4) pH of Strong Aqueous Acids & Bases
Strong acids dissociate completely
HCl(aq) → H+(aq) + Cl-(aq)
acid conj. base
A 1.0 M solution of HCl would produce 1.0 M H+
pH = -log [H+]
= -log[ 1.0M]
=0
What is the pH of a 1x10-5M solution of Mg(OH)2? (assume
completely soluble at this concentration)
2 mole of OH-/mole of Mg(OH)2
[OH-] = 2x10-5 What is the pH?
pOH = -log[2x10-5] pH = 14 – 4.7 = 9.3
pOH = 4.7
5) pH of Weak Aqueous Acids & Bases
Problem 1: Find the Ka of acetic acid if a 0.10 M
CH3COOH(aq) solution has a pH = 2.9.
Problem 2: What is the pH of a 0.01 M solution
of trimethylamine (CH3)3N? (Kb = 6.5 x10-5).
http://www.youtube.com/watch?v=bSQ7nxjmXXg&feature=related
Shortcut for Problem 2?
[(CH 3 ) 3 NH + ][OH − ]
Kb = = 6.5x10−5
[(CH 3 ) 3 N]
−5 x*x
6.5x10 = cross out - x from denominator
0.01− x
−5 x*x
6.5x10 =
0.01
x = 8.06x10−4
8.06x10−4 Compare to
Check : *100 = 8% 7.74x10-4
0.01
8% >5% so you cannot use shortcut
€
Weak Aqueous Acids/Conj. Bases
Ka is the equilibrium constant for a weak acid dissociating in
water to form its conjugate base.
HClO2(aq) ↔ H+(aq) + ClO2- (aq) Ka =
(
!" H + #$!"ClO2− #$)
[ HClO 2 ]
Stronger weak acids have higher [H+], higher pKa=-logKa
Ka, (and lower pKa)
Kb is the equilibrium constant for a weak base accepting a
proton from water to form its conjugate acid. ( [OH − ][HClO ])
2
Kb =
ClO2- (aq) + H2O(l) ↔ HClO2(aq) + OH-(aq) [ClO ] −
2
Stronger weak bases have higher [OH-], higher pKb=-logKb

Kb, (and lower pKb) €
(Weak) Conjugate Acid/Base Pairs
Acid pKa Conj. Base pKb
HCl -3 Cl- 17
HClO2(aq) ↔ H+ (aq)+ ClO2 -
(aq) Ka
HNO3 -1.3 NO3- 15.3
ClO2- (aq) +H2O(l) ↔ HClO2(aq) +OH-(aq) Kb H3O+ 0 H2O 14
HSO4- 1.9 SO4-2 12.1

H2O(l) ↔ H+ (aq) + OH-(aq) Kw
HF 3.2 F- 10.8
Ka*Kb = Kw CH3COOH 4.76 CH3COO- 9.24
H2CO3 6.3 HCO3- 7.7
H2S 7.04 HS- 6.96
Ka * K =
b
(!" H +
) (
#$!"ClO2− #$ !"OH − #$!" HClO2 #$
*
) HCN 9.2 CN- 4.8
!"ClO2− #$ NH4+ 9.25 NH3 4.75

[ HClO 2 ]
HCO3- 10.33 CO3-2 3.67
= !" H #$
+
* !"OH #$ = Kw
−
H2O 14 OH- 0
NH3 23 NH2- -9
pKa + pKb = pKw = 14 The stronger an acid,

the weaker its conj. base
6) Acid Strength: When the difference is away
from the bond broken…….. Electronegativity
An inductive effect that withdraws electron density from an

O-H bond increases the acidity of the compound
HOX Electronegativity of X pKa

HOCl 3.0 7.40
HOBr 2.8 8.55
HOI 2.5 10.5
Acid Strength: (Action away
from the bond broken)
Resonance
HOCl pKa 7.4
The more the negative charge

on the conj. base can be
shared through resonance, the
HOClO pKa 1.96
stronger the acid.
HOClO2 pKa -2
HOClO3 pKa -7.3

Fig 16.15 [online image].Retrieved October 12, 2016 from http://2012books.lardbucket.org/books/principles-of-general-chemistry-v1.0/s20-03-molecular-structure-and-
acid-b.html
Acid Strength: Different bonds broken… Bond
Polarity going across a period
HF > H2O >> H3N >>> CH4
Often need to explain data
rather than predict
Acid Strength: Different bonds broken… Bond
Enthalpy going down a group
HI > HBr > HCl> HF

Bond Bond
Enthalpy length Why is this different from
(kJ/mol) (pm) HOI<HOBr<HOCl where
H-F 568 92 the more electronegative
the halogen, the stronger
H-Cl 432 127 the acid?
H-Br 366 141
H-I 298 161
Predicting/explaining acid strength
If comparing away from bond broken (many
acids have OH bond broken)
-Electronegativity (greater EN, stronger acid)
-Resonance (more resonance, stronger acid)
If comparing different H-X bonds broken
-Across row (more EN atom, stronger acid)
-Down column (larger atom, stronger acid)
7) Identifying acid and bases
Salts
Anion
Cation
basic
ammonium neutral all others
acidic: amphoteric
R3NH+ conj. base strong
metal HSO4- H at front of ion
acidic acid
Cl-, NO3- HS-, HCO3-
Gp1, Gp2, +1
neutral d, p ≥+2
acidic Molecular
H+, anion
Binary oxides HCl, H2SO3 From Organic
acidic
Metallic Molecular carboxylic acid
Na2O amine
CO2 RCOOH
basic (CH3)2NH
acidic
basic
Identifying Binary Oxides as Acids & Bases
Acidic (molecular) oxides: react with water to

form a Bronsted acid; also react with bases
CO2(aq) + H2O(l) ® H2CO3(aq)
NaOH(aq) + CO2(g) ® NaHCO3(aq)
Basic (ionic) oxides: react with water to form a

Bronsted base; also react with acids
CaO(s) + H2O(l) ® Ca(OH)2(aq)
MgO(s) + 2HCl(aq) ® MgCl2(aq) + H2O(l)
Acid oxides
Amphoteric Li BeO B C N O
Oxides Na Mg Al2O3 Si P S
K Ca Ga2O3 GeO2 As2O3
(can act as an Rb Sr In2O3 SnO Sb2O Te
acid or base) SnO2
Cs Ba d block PbO Bi2O3 Po
PbO2
Basic Oxides
Al2O3(s) + 6 HCl(aq) ® 2 AlCl3(aq) + 3 H2O(l)

basic oxide; neutralizes acid
2 NaOH(aq) + Al2O3(s) + 3 H2O(l) ® 2 Na[Al(OH)4](aq)

acidic oxide; reacts with base
You do not need to memorize the amphoterics, just know general areas.
Identifying Salts as Acids or Bases: Look at Anion and Cation
Identifying Anions as Aqueous Acids & Bases

Neutral
Conj. Base of strong acids Cl-, Br -, I-, NO3-, ClO4-
Acidic HSO4-
Amphoteric
conj. base of polyprotic acid H2PO4-, HS-, HCO3-
HS-(aq) Û H+(aq) + S-2(aq) HS-(aq) + H2O(l) Û OH-(aq) + H2S(aq)
Basic
O-2, OH-, NH-2 strong bases
Conj. Base of weak acids F-, S-2, CN-, CO32-, PO43-, NO2-, CH3CO2-
F-(aq) + H2O(l) Û HF(aq) + OH-(aq)
Identifying Cations as Aqueous Acids & Bases
Basic None
Neutral
Gp 1 and 2 cations Li+, Na+, K+, Mg+2, Ca2+, Ag+, Cu+
Other metal cations +1
Acidic
“Ammonium” cations NH4+, CH3NH3+, C6H5NH3+
first row d block or p block Fe+3 as Fe(H2O)63+
+1 < charge Cr+3 as Cr(H2O)63+
Al+3 as Al(H2O)63+
Cu+2 as Cu(H2O)62+
Ni+2 as Ni(H2O)62+
Fe(H2O)63+(aq) + H2O(l) Û H3O+(aq) + Fe(H2O)5(OH-) 2+(aq)

d and p block +2 and +3 small metal ions in water
Greater charge;
Smaller cation radius;
Stronger coordination effect
“Figure 16.9.1: Effect of a Metal Ion on the Acidity of Water” Acid Base Properties of Salt Solutions. LibreTexts. 29 Aug 2017,
https://chem.libretexts.org/LibreTexts/University_of_Missouri/MU%3A__1330H_(Keller)/16%3A_Acid%E2%80%93Base_Equilibria/16.09%3A_
Acid-Base_Properties_of_Salt_Solutions
“Figure 16.9.2: The Effect of the Charge and Radius of a Metal Ion on the Acidity of a Coordinated Water Molecule” Acid Base Properties of Salt
Solutions. LibreTexts. 29 Aug 2017,
Metal cations as Bronsted acids in water
acid base conj. base conj. acid
Ka Ka Ka
Fe+3 6x10-3 Al+3 1x10-5 Zn+2 1x10-9
Sn+2 4x10-4 Cu+2 3x10-8 Co+2 2x10-2
Cr+3 1x10-4 Pb+2 3x10-8 Ni+2 1x10-10
Acid Base Properties of Salt Solutions. LibreTexts. 29 Aug 2017,
Problem 3:
64) Circle the pH range for each for the following 0.154 M aqueous solutions.
SO3 pH < 7 pH ~7 pH > 7 HIO3 pH < 7 pH ~7 pH > 7
Cu2CO3 pH < 7 pH ~7 pH > 7 C6H5NH3Br pH < 7 pH ~7 pH > 7
TiCl3 pH < 7 pH ~7 pH > 7 NiNO3 pH < 7 pH ~7 pH > 7

8) pH of a salt
Problem 4: What are the concentrations of all ions in a 0.1
M solution of KF? pKa HF = 3.45
9) Polyprotic acids and bases
H2SO3 Û HSO3- + H+ Ka1 = 1.7 x10-2
HSO3- Û SO3-2 + H+ Ka2 = 6.4 x10-8
HSO3- is amphiprotic & amphoteric
[online image] Retrieved October

17, 2016 from
http://faculty.sdmiramar.edu/fg
arces/zCourse/All_Year/Ch100_
OL/aMy_FileLec/04OL_LecNotes
_Ch100/10_AcidBase/1001_Acid
Base/1001_AcidBase.htm
Problem 5: pH of H2SO4
(the strong polyprotic)
Problem 6: 0.05 M H3PO4 find concentrations of all ions
10) van’t Hoff i factor and the effect of diluting an aqueous acid
Problem 7: What is the “i” factor for 10.0 mL of a 0.15 M

solution of HNO2 (Ka = 4.3x10-4)?
Problem 8: What are the pH and i factor for 10.0 mL of a 0.15
M solution of HNO2 (Ka = 4.3x10-4) after it is diluted to 1 L?
Estimating van’t Hoff i for weak acid/base
Molecular solutes i = 1
1-directional arrow “i" is an integer value

– Salts dissociating completely:
NaCl(aq) à Na+(aq) + Cl-(aq) i = 2
– Strong acid (dissociating completely)
HCl(aq) à H+(aq) + Cl-(aq) i = 2
Equilibrium arrow, “i” is ”in between”

HF(aq) ↔ H+(aq) + F-(aq) 1 < i < 2
Problem 9: Estimate the “i“ value (ie = 2, 2<i<3) for the
following solutes in water:
a) AgClO4
b) Cl2
c) K2O
Problem 9 (continued): Estimate the “i“ value (ie = 2,
2<i<3) for the following solutes in water:
d) H2SO4
e) Na2SO3
known Topic 09 Acid/base Mixtures
1) PUG Tables (when acid or base is strong)
2) Titration
A. Step by step (weak acid/strong base)
a) Pre ½ SP
b) ½ SP
c) ½ SP to SP
d) Stoichiometric point (SP)
e) Post SP
B. Indicators
C. Comparing titration curves
D. Polyprotic Titrations
3) Buffers
A. Definition
B. Factor of 10
C. Recipes
D. Adding strong acid or base
unknown
PUG for Acid plus
Base*
10.0 mL of a 0.08 M solution of NaOH(aq) is

mixed with 15 mL of a 0.1 M solution of HCl(aq).
What is the resulting pH?
*At least one of the acid and base must be strong

PUG for Acid plus
Base*
10.0 mL of a 0.08 M solution of NaOH(aq) is

mixed with 15 mL of a 0.1 M solution of HCl(aq).
What is the resulting pH?
Rxn (net ionic): H+ + OH- à H2O

Put in (moles): 0.0015 0.0008
Use up (limiting): -0.0008 -0.0008
Get out (must get a 0): 0.0007 0
pH = -log[H+] = -log [(0.0007mol/0.025L)] = 1.55
*At least one of the acid and base must be strong

strong weak weak strong strong strong
acid base acid base acid base
H + + B à HB+ HA + OH- à A- + H2O H+ + OH- à H2O
P
U
G
weak acid & conj. base weak acid OR conj. base

strong acid (plus weak acid)
B and HB+ HB+ strong base (plus weak base)
ICE with B + H2O ßà HB+ + OH- ICE with HB+ ßà H+ + B-
Use Kb to solve Use Ka to solve Find [H+] or [OH-] and then pH
HA and A-
A-
ICE with HA ßà H+ + A-
ICE with A- + H2O ßà HA + OH-
Use Ka to solve
Use Kb to solve
known Titrations
A titration is an analytical technique where an
unknown concentration of a substance is
determined via a chemical reaction by the addition
of a known amount of a known concentration of a
substance that reacts with the unknown.
A burette, a piece of graduated glassware, allows
the volume of the known to be measured.
The equivalence point/stoichiometric point occurs
when moles of added known substance have
stoichiometrically reacted with the moles of the
unknown substance (the reaction is complete.)
An indicator is used to tell when the equivalence
point has been reached.
unknown
known Study the titration of a weak acid (in the
beaker) with a strong base (in the buret).
*there must always be a strong in the
buret
0 mL KOH added what is pH in the beaker?
HA Û H+ + A- −4 x2
K a = 4.3x10 =
0.10 − x
I 0.1 0 0 x * = 6.6x10 −3
C -x +x +x *shortcut not OK x = 6.6% of 0.1
E 0.1-x x x by quad x= 6.35x10 -3 = [H + ]
pH =2.2
15 mL of 0.10 M solution of HNO2 (Ka =

-4
5 mL of 0.08 M KOH(aq) is added to 15 mL of 0.10 M HNO2(aq)
(Ka = 4.3x10-4, pH = 2.2) what is new pH?
" 0.1molHNO2 %
0.015L$ ' = 0.0015mol HNO 2
# L &
" 0.08molOH − % -
0.005L$ ' = 0.0004mol OH
# L &
http://dogtime.com/puppies/42559-pug-
puppies#/slide/1
HA + OH- ® H2O + A-
Use Put in 0.0015 0.0004 0 0
moles
Use up -0.0004 -0.0004 +0.0004
Get out 0.0011 0 0.0004
/0.02 L /0.02 L
HA Û H+ + A- −4
K a = 4.3x10 =
x(0.02 + x)
(0.055 − x)
I 0.055 0 0.02
by quad x = 1.098x10−3
C -x +x +x
E 0.055-x x 0.02 +x pH = 2.96
15 mL of 0.10 M solution of HNO2 (Ka = 4.3x10-4) titrate with
0.08 M KOH; 9.375 mL KOH added what is pH?
" 0.1molHNO2 %
0.015L$
# L
' = 0.0015mol HNO 2
&
1/2 stoichiometric point
" 0.08molOH − % -
0.009375L$ ' = 0.00075mol OH
# L & http://marketplace.akc.org/puppies/pug
HA + OH- ® H2O + A-
Put in 0.0015 0.00075 0 0
Use up -0.00075 -0.00075 +0.00075
Get out 0.00075 0 0.00075
/0.024375 L /0.024375 L
x(0.0308 + x)
HA Û H+ + A- K a = 4.3x10−4 =
(0.0308 − x)
I 0.0308 0 0.0308 x = 4.3x10−4

*shortcut OK x = 4.3x10 -4 M 1.4% of 0.0308
C -x +x +x
pH = 3.37 = pK a
E 0.0308-x x 0.0308+x
Distribution Diagram
Which point is the ½ stoichiometric point?
HNO2 NO2-
1
0.9
0.8
0.7
0.6
1/2 stoich point
pH = pKa
fraction
0.5
0.4
0.3
[HA]=[A-]
0.2
0.1
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15
pH
0.08 M KOH; 15 mL KOH added what is pH?
" 0.1molHNO2 %
0.015L$ ' = 0.0015mol HNO 2
# L &
" 0.08molOH − % -
0.015L$ ' = 0.0012mol OH
# L &
HA + OH- ® H2O + A-
Put in 0.0015 0.0012 0 0
Use up -0.0012 -0.0012 +0.0012
Get out 0.0003 0 0.0012
/0.03 L /0.03 L
HA Û H+ + A- K a = 4.3x10−4 =
x(0.04 + x)
(0.01− x)
I 0.01 0 0.04 x = 1.075x10−4
C -x +x +x *shortcut OK x = 1.075x10−4 1.1% of 0.01
E 0.01-x x 0.04 +x pH = 3.96
0.1M HNO2 titrated with 0.08M KOH
14
Known 12
[KOH] =
10
0.08 M
8
pH
6
3.96
4
2.96 3.37
2.2 2
0
0 5 10 15 20 25 30
mL of KOH added
KOH pH
0 mL 2.2
5 mL 2.96
A moles OH-added < moles HA 9.375 mL
[HNO2] HA Û H+ + A- 3.37
= 0.1 M 15 mL
3.96
15 mL of 0.10 M solution of HNO2 (Ka = 4.3x10-4)
titrate with 0.08 M KOH; 18.75 mL KOH added
what
0.015L$
# L
is '&pH?
" 0.1molHNO %
2
= 0.0015mol HNO
stoichiometric
2
point
" 0.08molOH − % - https://www.greenfieldpuppies.com/pug-puppies-for-sale/
0.01875L$ ' = 0.0015mol OH
# L &
HA + OH- ® H2O + A-
Put in 0.0015 0.0015 0 0
Use up -0.0015 -0.0015 +0.0015
Get out 0 0 0.0015
/0.03375 L
−14 2
1x10 x
A- + H2O Û HA + OH- K b = 4.3x10−4 = 2.33x10 = (0.044 − x)
−11
I 0.044 0 0 *shortcut OK
C -x +x +x x = 1.016x10−6 2x10−7 %of 0.044M
E 0.044-x x x [OH − ]= 1.106x10−6

pOH = 5.99;pH = 8
14
Known 12
[KOH] 10
= 0.08 8.00
B
8
M pH
6
0
0 5 10 15 20 25 30
Stoichiometric
mL of KOH added
molespoint
OH-added = moles HA
HA(aq) + OH-(aq) ® H2O(l) + A-
Goes to all products
A- + H2O Û HA + OH-
[HNO2] pH >7 due to A-
0.08 M KOH; 20 mL KOH added what is pH?
" 0.1molHNO2 %
0.015L$ ' = 0.0015mol HNO 2
# L &
" 0.08molOH − % -
0.020L$ ' = 0.0016mol OH
# L &
https://www.greenfieldpuppies.com/pug-puppies-for-sale/
HA + OH- ® H2O + A-
Use
moles Put in 0.0015 0.0016 0 0
Use up -0.0015 -0.0015 +0.0015
Get out 0 0.0001 0.0015
/0.035L
excess OH- rules
x from A- + H2O Û HA + OH- equilibrium to small to
impact OH-
[OH-] = 0.0001 mol/0.035L = 0.0029M
pH =11.46
excess OH- rules
C moles OH-added > moles HA
Known
[KOH] =
0.08 M 0.1M HNO2 titrated with 0.08M KOH
14
C
12
10
11.46
8
pH
0
0 5 10 15 20 25 30
mL of KOH added
[HNO2] = 0.1 M
Acid/Base Titration
Need at least one strong partner
Use net ionic equation in PUG (in moles)
HA + OH- ® A- + H2O
B + H+ ® HB+
H+ + OH- ® H2O
Get out:
If H+ or OH- (and a monoprotic acid/base) find [ ] then pH
If weak acid and/or base go to ICE or HH**
At SP: moles of reactants are equal; Get out row 0, 0

At ½ SP*: moles strong base (OH-) = ½ moles acid (HA)
Get out: moles acid (HA) = moles conj.base (A-); pH=pKa
* for HA + OH- à A- + H2O
strong weak weak strong strong strong
acid base acid base acid base
H + + B à HB+ HA + OH- à A- + H2O H+ + OH- à H2O
P
U
G
weak acid & conj. base weak acid OR conj. base

strong acid (plus weak acid)
B and HB+ HB+ strong base (plus weak base)
ICE with B + H2O ßà HB+ + OH- ICE with HB+ ßà H+ + B-
Use Kb to solve Use Ka to solve Find [H+] or [OH-] and then pH
HA and A-
A-
ICE with HA ßà H+ + A-
ICE with A- + H2O ßà HA + OH-
Use Ka to solve
Use Kb to solve
The goal of most titrations is
to find the concentration of
the unknown.
A titration in which the analyte

initially consists of 25.00 mL of
NaOH(aq) and the titrant is 0.340 M
HCl(aq)
When 18.38 mL of HCl have been

added, the pH in the beaker is 7.0.
What is the concentration of the
Figure 21.19.1 [online image]. Retrieved
NaOH sample? October 18, 2016
fromhttp://chem.libretexts.org/Textbook_Maps
/Introductory_Chemistry_Textbook_Maps/Map
%3A_Introductory_Chemistry_(CK-
12)/21%3A_Acids_and_Bases/21.19%3A_Titr
ation_Curves
25.00 mL of x M NaOH(aq) is titrated with 0.340 M HCl(aq)
When 18.38 mL of HCl have been added, the pH in the beaker
is 7.0. What is the concentration of the NaOH sample?
" 0.340molH + % −3 +
0.01838L$ ' = 6.25x10 molH
# L &
OH- + H+ ® H2O
Use Put In x 6.25 x10-3 0
moles Use up -6.25 x10-3 -6.25x10-3 +6.25x10-3
Get out 0 0 6.25x10-3
[OH-]= 6.25x10-3mol/0.025L = 0.25 M
Use original volume

Indicators
(When do you reach the stoichiometric point?)
pH = 1 pH = 11
HIn ⇌ H + + In- + −
[H ][In ]
Figure 16.23 [online image]. Retrieved
October 18, 2016 from
Kin = http://2012books.lardbucket.org/books/p
Red Blue [HIn] rinciples-of-general-chemistry-v1.0/s20-

05-acid-base-titrations.html
pKin = pH of color change = endpoint (stop titrating)
Pick pKIn at a pH just past the stoichiometric point

Endpoint w/
phenolphthalein pKIn = 9.4
Stoichiometric point
Strong acid + strong base
pH = 7
Other Drawbacks
Judging the color change can be
subjective
Indicators must be used in very low Figure 21.19.1 [online image]. Retrieved October 18,
concentrations relative to the 2016
fromhttp://chem.libretexts.org/Textbook_Maps/Introduc
unknown solution to avoid changing tory_Chemistry_Textbook_Maps/Map%3A_Introductor
the equilibria y_Chemistry_(CK-
12)/21%3A_Acids_and_Bases/21.19%3A_Titration_C
urves
North Carolina School of Science and Mathematics. Distance Education and Extended
Programs. Teachers’ Instructional Graphics Educational Resources.
http://www.dlt.ncssm.edu/tiger/chem6.htm (Accessed Nov 11, 2015.)
Titration of 40.0 mL of 0.1 M NH3
with 0.100 M HCl
Hydrangeas
Blue = acid soil Pink = Basic soil
Color change actually happens due to different solubility of

nutrients at different pHs
Most indicators are naturally occurring organic acids
Effect of pKa on a titration curve
Titration of 50.0
mL of 0.1 M HA
with 0.10 M
NaOH
a) pKa = 1
b) pKa = 3
c) pKa = 5
d) pKa = 7
e) pKa = 9
f) pKa = 11
Harvey, D. (2016) 9.2 Acid-Base Titrations: Figure 9.10. Retrieved from:

https://chem.libretexts.org/Textbook_Maps/Analytical_Chemistry_Textbook_Maps/Map%3A_Anal
ytical_Chemistry_2.0_(Harvey)/09_Titrimetric_Methods/9.2%3A_Acid%E2%80%93Base_Titratio
ns
Polyprotic Acid
Titrations:
H3PO4 with PO4-3
Strong Base
[online image]. Retrieved October 18

2016 from
http://www.mlane.us/photo/h/h3po4-
titration-curve/11/
Polyprotic Acid Titrations: H3PO4 titrated w/ NaOH
H3PO4 + OH- ® H2PO4- + H2O

1/2 stoichiometric point 1:
Put In: mole OH- = 1/2 moles of H3PO4
Get out: moles H3PO4 = moles H2PO4-
pH = pKa1 = 2.12
Stoichiometric point 1:
Put In: mole OH- = moles of H3PO4
Get out: all H2PO4-
H2PO4- + OH- ® HPO4-2 + H2O

For ½ stoichiometric point 2 and stoichiometric point 2
HPO4-2 + OH- ® PO4-3 + H2O

For ½ stoichiometric point 3 and stoichiometric point 3
SP1 SP2 SP3
½SP1 ½SP2 ½SP3
[online image]. Retrieved October 18, 2016 from: http://ion.chem.usu.edu/~sbialkow/Classes/3600/Overheads/H3A/H3A.html

polyPUG for polyprotic
H2S + OH- -> H2O + HS-
P 1 mol 1.5 0
U
G
HS- + OH- -> H2O + S-2
P
U
G
Buffers
A buffer is a solution in which the pH resists change when
small amounts of strong acids or bases are added because it
contains both a weak acid (proton source) and its conjugate
base (proton sink) HA ⇌ A- + H+
(aq) (aq) (aq)
proton source
HA H+ Add OH- H+ A- HOH

A- A-
HA dissociates
A- H HA
+ A- H+ HA
HA HA HA HA
proton sink pHbox 1 ≈ pHbox2
HA H+ HA H+
A- HA
A- H+ HA Add H+
A- H+ HA
HA HA HA HA
Buffering Region of a Weak Acid
The buffering region is the range over which an added OH- or H+ does
not significantly change the pH of a weak acid/conj.base solution.
[pKa of the weak acid ± 1 pH unit]
Weak acid/strong base titration curve

14
12
10
8
Stoichiometric point
pH
6
Buffering region
4
0
0 5 10 15 20 25 30
mL of KOH added
½ SP SP
Polyprotic Acids as Buffers?
Polyprotic acids have multiple buffering regions (multiple ½ SP)
Example: carbonic acid
1) H2CO3(aq) ⇌ H+(aq) + HCO3- (aq)pKa1 = 7
HA = H2CO3 A- = HCO3-
2) HCO3-(aq) ⇌ H+(aq) + CO32-(aq) pKa2 = 10

HA = HCO3- A- = CO32-
Henderson–Hasselbalch Equation
(ICE + shortcut for buffer solutions)
HA(aq) ↔ H+(aq) + A-(aq) (x)(0.1+ x)
Ka =
I 0.2 0 0.1 (0.2− x)
C –x +x +x
⎛ [x][0.1+ x]⎞
E 0.2-x x 0.1+x −log K a = −log ⎜
⎝ [0.2− x] ⎟⎠
[H + ][A− ] (x)(0.1+ x)
Ka = = [0.1]
[HA] (0.2− x) pK a = −log[x]− log
[0.2]
Shortcut* = (x)(0.1+ x) [A− ]initial

(0.2− x) pK a = −log[H + ]− log
[HA]initial
*Use shortcut b/c Ka is small AND initially there is a

significant quantity of products so x is v. small.
Henderson–Hasselbalch Equation
[A− ]initial
pK a = −log[H + ]− log
[HA]initial
[A− ]
pK a = pH − log
[HA]
1) Limit: [A-] and [HA] are w/i a factor of 10 of one another:

0.1 < [A-]/[HA] <10
2) Ideal implies no interactions among ions
Factor of 10:
−
[A ]
0.1 < < 10 OR pH = pKa +/- 1
[HA]
[A- ]
0.1 0.4 0.6 1 4 6 10
[HA]
pKa - 1……… pKa………… pKa + 1
€ [HA] = 10*[A-] 10*[HA] = [A-]

Buffer capacity is the maximum amount of acid or base
that can be added before the buffer loses its ability to
resist large changes in pH (goes outside of the factor of
10 range.)
A more concentrated buffer has a higher buffer capacity than

a less concentrated buffer
3 Recipes for Buffers
1) Mix weak acid/conj base pair
[mol OR g OR (mL of M solution)] NH4+ as NH4Cl
+ [mol OR g OR (mL of M solution)] NH3
2) Add strong acid to weak base

add HCl to NH3 to convert some* to NH4+
3) Add strong base to weak acid

add NaOH to NH4+ to convert some* to NH3
*[NH3] and [NH4+] are w/i a factor of 10 in a buffer solution

Problem 1: How would you prepare an ammonia (pka = 9.25) buffer
using NH4Cl and 6M NH3 with a pH of 10 that has a total concentration
of 0.2 M ammonia species and a total volume of 500 mL?
Problem 1: How would you prepare an ammonia (pka = 9.25) buffer
using NH4Cl and 6M NH3 with a pH of 10 that has a total concentration
of 0.2 M ammonia species and a total volume of 500 mL?
[A − ]
pH = pK a + log
[HA]
[A − ]
10 = 9.25 + log
[HA]
[A − ]
10 0.75 =
[HA]
5.62[HA] = [A − ]
0.03molNH 4+ " 0.5L %" 53.5gNH 4 Cl %
$ '$ + ' = 0.8025gNH 4 Cl
L # &# 1molNH 4 &
[HA] + [A − ] = 0.2
[HA] + 5.62[HA] = 0.2
+
[HA] = 0.03M = [NH 4€ ] 0.17molNH 3 " 0.5L % " 6molNH 3 %
$ ' = 0.085molNH 3 = xL$ '
[A − ] = 0.17M = [NH 3 ] L # & # L &
0.0147L = 14.7mL = x = volume NH 3
What would be the resulting pH of the buffer on the
previous slide if 0.001 moles of solid NaOH were added?
NH4+ +OH- ® NH3 H2O

P 0.03M*0.5L 0.001mol 0.17M*0.5L
=0.015mol = 0.084 mol
U
G
What would be the resulting pH of the buffer on the
previous slide if 0.001 moles of solid NaOH were added?
NH4+ +OH- ® NH3 H2O

P 0.03M*0.5L 0.001mol 0.17M*0.5L
=0.015mol = 0.084 mol
U -0.001 mol -0.001mol +0.001 mol
G 0.014mol 0 0.085 mol
[A− ]
pH = pK a + log
[HA]
Use moles or M in
# 0.085mol &
%$ 0.5L (' HH equation since
pH = 9.25 + log both A- and HA
# 0.014mol &
%$ 0.5L (' have the same
volume.
= 10.03
What would be the resulting pH of the buffer if 30 mL of
a 1.0 M HCl solution was added to the original buffer?
NH3 + H+ ®NH4+
P 0.084mol 0.03mol 0.015 mol
U -0.03 mol -0.03mol +0.03 mol
G 0.054mol 0 0.045 mol
" 0.054mol %
$# 0.53L '&
pH = 9.25 + log
" 0.045mol %
= 9.3 ΔpH = 9.3 −10 = −0.7
$# 0.53L '&
How would the pH of water change if the same amount of

€ HCl was added to 500 mL
€ of pure water?
ΔpH = 1.25 − 7 = −5.75
Topic 10 Electrochemistry
1) Oxidation numbers 10) Electrical work
2) Gotta Know terms 11) DGo, K, DEo
3) Balancing Redox in Acid 12) Nernst Equation
or Base (DGtoeq, Q, DE)
4) Activity Series 13) Electrolytic cells/
5) Electrochemical Cell electroplating
6) Standard Reduction 14) Current
Potentials Eo 15) Power
7) DEo 16) Corrosion
8) Why not to multiply Eo 17) Redox titration
9) Cell line notation
1) Oxidation Numbers
Oxidation state (or oxidation number) system that allows
tracking of the movement of electrons in reactions
2 Fe(s) + 3 Cl2(g) ® 2 FeCl3(s)
2 Fe0 ® 2 Fe3+ + 6 e-
6 e- + 6 Cl0 ® 6 Cl-1
Redox reactions involve the transfer of electrons from

one reactant to another. The reaction energy can be
harnessed in the form of electricity.
The branch of chemistry that deals with the relationship

between electricity and chemical reactions is called
electrochemistry.
Inorganic Method for Oxidation Numbers
1. An atom in its elemental form has a 0 oxidation state.
2. The oxidation number of a monatomic ion equals the
charge on the ion.
3. Specific elements*
a) The oxidation state of oxygen is almost always -2. The
only major exception is in peroxides (H-O-O-H), where
oxygen has an oxidation state of -1.
b) The oxidation state of hydrogen is +1 when bonded to
non-metals and -1 when bonded to metals.
c) The oxidation state of fluorine is always -1.
4. The sum of the oxidation states of all atoms in a neutral
compound must equal 0. The sum of the oxidation
states of all atoms in a polyatomic ion equals the charge
of the ion.
Organic Method:
For each covalent bond, assign the more electronegative
atom a “–” and the less electronegative atom a “+”;
Sum up charges and add in formal charge)
Warm up: CF4
Oxygen’s oxidation: H2O vs H2O2
Double bond and formal charge: ClO4- NO3-

2) Electrochemistry Gotta Know Terms
0 +1 -2 +1 0 -2 +1
2Na(s) + 2H2O(l) ® 2Na+ (aq) + H2(g) + 2OH-(aq)
An atom is oxidized when it loses an electron/s

An atom is reduced when it gains an electron/s
An oxidizing agent brings about oxidation

(it gets reduced)
A reducing agent brings about a reduction
(it gets oxidized)
LEO GER OIL RIG
3) Balancing Redox Reactions
1) Divide the net ionic reaction into oxidation and
reduction half reactions
2) For each half reaction
a) Balance all elements except oxygen and hydrogen.
b) Balance the oxygens by adding water.
c) Balance hydrogens using H+
d) Balance the electrons
e) Check charge balance and elemental balance
3) Combine the balanced half reactions
4) If in base add one OH- for every H+ to both sides of the
equation
5) Simplify and check
Balancing a Redox Reaction
Zn(s) + NO31-(aq) ® Zn(OH)42-(aq) + NH3(aq)
1) Divide the full reaction into its oxidation and reduction half
reactions
1 elements
2 O with H2O
3 H with H+
4 e-
ü
8 e- + 9H+ + NO3- ® NH3 + 3 H2O
4 H2O + Zn ® Zn(OH)4-2 + 4H+ + 2e-
3) Combine the balanced half reactions to “hide” the electrons
4) If in base add one OH- for every H+ to both sides of the equation
7 OH- + 6H2O + 4 Zn + NO3- ® 4Zn(OH)4-2 + NH3

Balancing a Redox Reaction in Base
4) If in base add one OH- for every H+ to both sides of the equation
13 H2O + 4 Zn + NO3- ® 4 Zn(OH)4-2 + 7 H+ + NH3
7 OH- + 6H2O + 4 Zn + NO3- ® 4 Zn(OH)4-2 + NH3

H2O2(aq) + Cl2O7(aq)®ClO2 (aq) + O2(g)
-
(in base)
1 elements
2 O with H2O
3 H with H+
4 e-
ü
H2O2(aq) + Cl2O7(aq)®ClO2 (aq) + O2(g) -
(in base)
4*( H2O2(aq) ® O2(g) + 2H+ + 2e- )

4H2O2(aq) ® 4O2(g) + 8H+ + 8e-
8e- + 6H+ + Cl2O7(aq) ® 2ClO2-(aq) + 3H2O

4H2O2(aq) + Cl2O7(aq) ® 4O2(g) + 2H+ + 2ClO2-(aq) +3H2O
2 OH- 2 OH-
4H2O2(aq) + Cl2O7(aq) + 2OH-(aq)® 4O2(g) + 2ClO2-(aq) +5H2O

4) Oxidation of metals;
Reduction of metal cations
Cu(s) à Cu+2(aq) + 2e-
Ag+(aq) + e - à Ag(s)
Cu(s) + 2Ag+(aq) à Cu+2(aq) + 2Ag(s)

Bruce Averill and Patricia Eldredge. General Chemistry: Principles, Patterns, and
Applications, v. 1.0 (2 Volume Set)
http://catalog.flatworldknowledge.com/bookhub/4309?e=averill_1.0-ch04_s08
Concept Question 4: Activity Series
Mg+2(aq) Cu+2(aq) Ag+(aq) Fe+2
Ag(s) NR NR NR
Cu(s) NR Ag forms on Cu NR
Mg(s) Cu forms on Mg Ag formed on Mg Fe forms on Mg
Fe(s) NR Cu forms on Fe Ag forms on Fe
i) Which metal is easiest to oxidize?

(is most reactive)
ii) Which metal ion is easiest to reduce?
A) i) Mg ii) Ag+
B) i) Ag ii) Mg2+
C) i) Ag ii) Cu2+
D) i) Fe ii) Ag+
Concept Question 4: Activity Series
Mg+2(aq) Cu+2(aq) Ag+(aq) Fe+2
Ag(s) NR NR NR
Cu(s) NR Ag forms on Cu NR
Mg(s) Cu forms on Mg Ag formed on Mg Fe forms on Mg
Fe(s) NR Cu forms on Fe Ag forms on Fe
i) Which metal is easiest to oxidize? (is most reactive)

ii) Which metal ion is easiest to reduce?
A) i) Mg ii) Ag+
Ag+ + e- à Ag(s)
B) i) Ag ii) Mg2+ Cu+2 + 2e- à Cu(s)
C) i) Ag ii) Cu2+ Fe+2 + 2e- à Fe(s)
Mg+2 + 2e- à Mg(s)
D) i) Fe ii) Ag+
4) Activity Series
5) Electrochemical Cells
1. The anode: the
compartment where Porous barrier
oxidation occurs.
2. The cathode: the
compartment where
reduction occurs.
3. External pathway to
allow the flow of
electrons. (This can
include a light bulb,
voltmeter, motor, etc.) Anode
Zn ® Zn+2 + 2e-
4. Salt bridge or porous
barrier: allows ions to flow Cathode
back and forth so that Cu+2 + 2e- ® Cu
charge does not build up.
Zn ® Zn+2 + 2e- Cu+2 + 2e- ® Cu
Zn(s)│Zn+2(aq) ││Cu+2(aq)│Cu(s)
anode salt bridge cathode
Figure 19.3 [Online image]. Retrieved November 8, 2016 from https://saylordotorg.github.io/text_general-chemistry-principles-

patterns-and-applications-v1.0/s23-electrochemistry.html
6) Half-Cell Potential Eo
Cell potential (E) = measure of ability of a cell

reaction to force electrons through a circuit
Volt (SI unit for electrical potential); defined by Coulomb & Joule
SHE: Standard Hydrogen Electrode oStandard conditions:

1M, 1bar, 25oC
2 H+(aq) + 2e- ® H2(g) Eo = 0 V
reduction half cell potential 1 bar
We think of these as one directional, but

they are really in equilibrium
Hydronium version
2 H3O+(aq, 1.00 M) + 2e- Û H2 (g, 1 bar) + 2H2O(l)
Measuring Relative Potentials
2 H+(aq) + 2e- ® H2(g) reduction Eo = 0 V
Zn(s) ® Zn2+(aq) + 2e- oxidation Eo = 0.763 V
Spontaneous direction
+ potential
To get value for Zn/Zn+2 for the

standard reduction table, flip Zn
reaction; change sign
Zn2+(aq) + 2e- ® Zn(s)

Eo = -0.763 V
Likely to
be
reduced
(gain
electrons)
Likely to be
oxidized
(lose e-)
[online image] Retrieved June 7, 2017 from: http://ch302.cm.utexas.edu/images302/Electrochemistry_Reduction_Potentials.jpg
7) DEo From standard reduction potentials table:
Full Cell Potential Cu+2 + 2e- → Cu(s) Eo = 0.3419 V
Zn+2 + 2e- → Zn(s) Eo = -0.7618 V
Flip equation; change sign of E
Zn(s) → Zn+2 + 2e- Eo = 0.7618 V anode oxidation

Cu+2 + 2e- → Cu(s) Eo = 0.3419 V cathode reduction
____________________________________________
Cu+2 + Zn(s) → Zn+2 + Cu(s) DEo = 1.1037 V
Add equations; add Eo

DEo > 0, spontaneous, voltaic/galvanic cell
DEo < 0, nonspontaneous
You should NOT multiply an Eº value when finding ΔEo
Al(s) à Al+3 (aq) + 3e- 1.66 V

Cu+2(aq) + 2e- à Cu(s) 0.34 V
*2
2 Al(s) à 2 Al+3 (aq) + 6e- 1.66 V
*3
3 Cu+2(aq) + 6e- à 3Cu(s) 0.34 V
3 Cu2+(aq) + 2 Al(s) → 2Al+3(aq) + 3Cu(s) DEo = 2.00 V*
** Potentials can only be added for reactions where all

electrons cancel out.
Capturing Electrochemistry
• Electrochemical cell: A combination of
anode, cathode, and other materials arranged
so that a product-favored redox reaction can
cause a current to flow or an electric current
can cause a reactant-favored redox reaction
to occur
• Voltaic cell (battery): An electrochemical
cell or group of cells in which a product-
favored redox reaction is used to produce an
electric current.
• Galvanic cell: A spontaneous chemical
reaction produces electrical current
• Electrolytic cell: A cell where
nonspontaneous electrochemical reactions
are produced by applying electrical energy
8) Cell Line Notation
Anode ; Salt bridge ; Cathode
Zn(s) | Zn2+(aq) | | Cu2+(aq) | Cu(s
(Zn(s) ® Zn2+(aq) + 2 e-) (Cu2+(aq) + 2e- ®Cu(s))
Write all half reaction components in the order that they appear
Use | to show interface between phases
Use , in between components in the same phase
No need to include stoichiometric coefficients
Pressure/concentration may be included after phase symbol
Electrode is outermost component
Use Pt electrode if needed
Example :
Pt(s) | H2(g,1bar) | H+ (aq,0.01M) || Fe+3 (aq,1x10-5M), Fe+2 (aq,1M) | Pt(s)
H2(g) ® 2H+(aq) + 2e- Fe3+(aq) + e- ® Fe2+(aq)

9) G…why you never multiply E
Zn(s) → Zn+2(aq) + 2e- G1o = -nFE1o E1o = 0.76 V
= -147 kJ
flip
G2o = 147 kJ
Zn+2(aq) + 2e- → Zn(s) E2o = - 0.76 V
G2o = -G 1 = -nFE2o
multiply
o
G3 = 294 kJ E3
o = - G o/n F
3 3
2 Zn+2(aq)+ 4e- → 2 Zn(s) E3
o = - 2G o/2n F
2 2
G3 = 2*G2 E o = -G o/n F=E o
o
3 2 2 2
= -0.76 V
Potential (Eº or ΔEº) is an intensive property: it does not

depend on the amount of oxidizing agent or reducing agent
but rather what they are.
10) Electrical Work
we = charge* potential
= -Q* DE Q = nF
= - n F *DE n = moles of e- (cancelled out in
overall balanced equation)
F = 9.6485x104 C/mol e-
Faraday’s constant
w e = −nFΔE
96485C 1.602x10 −19 C 6.022x10 23 e − 96485C
− * =
= −n moles e * − *V e −
mole e −
mole e -
mole e
units : J = CV
€
DGT gives maximum non-expansion work associated with a
reversible system at constant P and T
DGo = welectrical = -nFDEo

11) DGo, K, DEo
DGo = -nFDEo
DGo = -RTlnK298 T = 298 K
-nFDEo= -RTln K298
RT
o 0.0592V
ΔE = ln K 298 = log K 298
nF n
DGo K298 DEo Reaction under standard conditions

<0 >1 >0 Spontaneous/ product favored
0 1 0 Reactants/products equally favored
>0 <1 <0 Nonspontaneous/ reactant favored

12) DGtoeq, DEtoeq, Q
DGto eq = 0
DGto eq = -nFDEto eq
DEto eq = 0
As the reaction progresses DGto eq < 0
towards products:
DEto eq > 0
Q < K and increasing
DE(to eq) positive going to 0 DGto eq > 0
DGto eq negative going to 0 DEto eq < 0
12) The Nernst Equation DGtoeq, DE, Q
ΔGtoeq = ΔG o + RT lnQ
o
−nFΔE(toeq) = −nFΔE + RT lnQ
−nFΔE o RT lnQ
ΔE(toeq) = +
−nF −nF
o 0.0592 V
ΔE(toeq) = ΔE − logQ
n
Reactants ê Products é
Qé ΔE(toeq) ê
Reactants é Products ê
Qê ΔE(toeq) é
DE = DEo - 0.0592 V log Q
n
n=2
Zn(s) + Cu2+(aq) Û Zn2+(aq) + Cu(s)
[Zn 2+ ]
DEo = 1.10 V Q=
[Cu 2+ ]
Ecell vs. log Q for zinc-copper cell
reactants or fewer products Qê DEé

More €
1.30
1.25
1.20
1.15 [Cu2+] >[Zn2+]
1.10
Ecell (V)
1.05
DE 1.00 Q = 1, DE = DEo
0.95
0.90 More products or fewer
0.85
0.80
reactants Qé DEê
-5 -4 -3 -2 -1 0 1 2 3 4 5
log Q [Zn2+] >[Cu2+]
Nernst: Potentials DE = DEo - 0.0592 V log Q
change with pH n
1
O2(g) + 4H+ (aq) + 4e- à 2H2O(l) Q=
PO2 [H + ]4
Eo = 1.23V; [H+] = 1M
[H+] = 1x10-7
0.0592 1
E = 1.23− log −7 4
= 0.82
4 (1)(1x10 )
E@pH = 7 = 0.82V [H+] down; Q up; DE down

Nernst Application: DE = DEo - 0.0592 V log Q
Concentration Cell n
Anode : Cu(s) ® Cu2+(aq)(0.001M) + 2 e- Eo = -0.34

Cathode: Cu2+(aq)(2.0 M) + 2 e- ® Cu(s) Eo = +0.34
Cu2+(aq)(2.0 M) + Cu(s) ® Cu2+(aq)(0.001M) + Cu(s)
2+
DE o = 0 V!
[Cuanode ] [0.001M] −4
Q= 2+
= = 5x10
[Cucathode ] [2.0M]
DE = DEo - 0.0592 V log Q Qê more reactants/

n fewer products
= 0 - 0.0592V log(5x10-4) DEé
2
= 0.097 V
Problem: How does potential DE change (immediately) upon..
Cathode: 2e - + 2H+(aq) + BrO-1(aq) à Br -1(aq) + H2O(l)

Anode: 2 H2O(l) + MnO2(s) à MnO4-1(aq) + 4 H+(aq) + 3 e-
Multiply to
cancel electrons
Cathode: 6e - + 6H+(aq) + 3 BrO-1(aq) à 3 Br -1(aq) + 3 H2O(l)
Anode: 4 H2O(l) + 2 MnO2(s) à 2 MnO4-1(aq) + 8 H+(aq) + 6 e-
Put into base
Cathode: 6e - + 3 H2O(l) + 3 BrO-1(aq) à 3 Br -1(aq) + 6 OH-(aq)

Anode: 8 OH-(aq) + 2 MnO2(s) à 2 MnO4-1(aq) + 4 H2O(l) + 6 e-
3 BrO-1(aq) + 2 MnO2(s) +2 OH-(aq) à 2 MnO4-1(aq) + 3 Br -1(aq) + H2O(l)
3 6 2
⎡ Br ⎤
−
⎡OH ⎤ −
⎡ MnO4 ⎤ −
⎣ ⎦ cat ⎣ ⎦ cat ⎣ ⎦
Q= 8 3
an
⎡OH ⎤−
⎡ BrO ⎤ −
⎣ ⎦ an ⎣ ⎦ cat
Problem: How does potential DE change (immediately) upon..
Cathode: 6e - + 3 H2O(l) + 3 BrO-1(aq) à 3 Br -1(aq) + 6 OH-(aq)

Anode: 8 OH-(aq) + 2 MnO2(s) à 2 MnO4-1(aq) + 4 H2O(l) + 6 e-
3 6 2
⎡ Br ⎤
−
⎡OH ⎤ −
⎡ MnO4 ⎤ −
⎣ ⎦ cat ⎣ ⎦ cat ⎣ ⎦
Q= 8 3
an
⎡OH ⎤ −
⎡ BrO ⎤ −
⎣ ⎦ an ⎣ ⎦ cat
a) Adding KBrO(s) to the cathode

b) Adding KBr(s) to the cathode
c) Adding insoluble MnO2(s) to the anode/cathode
d) Diluting both half cells with water to half their initial
concentrations.
e) Increasing the pH of the cell
f) Switch electrodes.
g) Changing the salt bridge from NaCl to KBr
13) Electrolytic cells
Fuel Cell vs. Electrolysis

Galvanic Electrolytic
2H2 + O2 → 2H2O 2H2O → 2H2 + O2

DEo = 1.23V DEo = -1.23V
Work out Work in
14) Current
Current (I) is the rate of charge flow: how
many electrons move between the electrodes
per second
Amperes (amps, A) 1 A = 1 C/s
Q is charge (replaced by n*F)

Q nF
n moles of e- (that actually flow I= =
through the circuit) t t
F is Faraday's constant It = nF
t is time (usually in sec (s))
€
How long would it take to electrolyze 1 mol of water using a
current of 2.5 A?
Overall reaction:
2 H2O(l) → O2 (g) + 2 H2(g) DEo = -1.23 V
anode (oxidation): 2 H2O(l) → O2(g) + 4 H+(aq) + 4e- Eo = -1.23 V

cathode (reduction): 4 H+ (aq) + 4 e- → 2 H2 (g) Eo = 0.0 V
⎛ 4mol e − ⎞ ⎛ 96485C ⎞ ⎛ s ⎞ ⎛ 1min ⎞ ⎛ 1h ⎞

1molH2O ⎜ ⎟ ⎜ − ⎟⎜ ⎟ ⎜ ⎟ ⎜ ⎟ = 21.4h
⎝ 2molH2O ⎠ ⎝ mol e ⎠ ⎝ 2.5C ⎠ ⎝ 60s ⎠ ⎝ 60min ⎠
Overpotential needed for electrolytic cells! Overpotential is the additional
potential difference that must be applied to reverse a non-spontaneous cell
reaction and achieve a significant rate of product formation.
w/ Pt electrode, electrolysis of water OP = 0.6 V

Apply 1.23 V + 0.6 V = ~1.8V
Electrolysis of water is facilitated by adding an electrolyte.

The electrolyte must be non-reactive* ie NaCl
Which is oxidized Cl- or H2O?
2H2O(l) → O2(g) + 4H+(aq)+ 4e- Eo = -1.23 V
2 Cl-(aq) → Cl2(g) + 2e- Eo = -1.36 V
*The reaction with the
most positive potential
Which is reduced Na+ or H+? is the one that will
2H+ (aq) + 2e- → H2(g) Eo = 0 V take place first.
Na+(aq) + e- → Na(s) Eo = -2.71 V
NaCl allows electrical conduction in water, but avoids being

oxidized/reduced by the overpotential needed for electrolysis.
13) Electroplating (nonspontaneously
reducing a metal cation)
How many moles of electrons does it take to

electroplate 0.3 mm of silver on an object with a
surface area of 36 cm2 from an Ag1+(aq) solution?
The density of silver is 10.5 g/cm3.
Ag1+ + e- ® Ag(s)
0.3mm ! 1cm $! 36cm 2 $! 10.5gAg $

# &# &# 3 & = 11.34gAg
" 10mm %" %" cm %
! 1molAg $! 1mol e− $ −
11.34gAg # &# + & = 0.105mol e
" 107.9gAg %" 1molAg %
[Ag+]
does not
change
n in electrochem
DGo = -nFDEo n is the number of moles of e- in

o 0.0592V overall equation; always an
ΔE = ΔE − logQ integer value
n
n is moles of electrons that

It = nF move through the circuit; rarely
an integer
15) Power and Work
Combining potential and current gives power, which
is energy per time
Incandescent
Power = I*ΔE 100W ~1000 hour life
$1-2
(units) = A*V J = CV
C J
= * Compact fluorescent
s C
7W, 8000 hour life
J
= = W (Watt) $1-2
s
LED
7W, 50000 hour life
€ ~$10
Alkaline Batteries: Aim for Constant DE
Zn(s) + 2 OH-(aq) → Zn(OH)2(s) + 2 e-
2 MnO2(s) + H2O(l) + 2 e- → Mn2O3(s) + 2 OH-(aq)
--------------------------------------------------------------------------------------------------------
Zn(s) + 2 MnO2(s) + H2O(l) → Zn(OH)2(s) + Mn2O3(s)
DE = DEo - 0.0592 V log Q

n
Alkaline refers to OH-(aq)
No net (aq) ions: constant ΔE
"Paste" instead of a liquid: dry cell
• Water is consumed, not used as solvent
• OH- act as "salt bridge" to balance half-
reaction charges
• Not rechargeable: products diffuse away from
the electrodes
16) Corrosion
Unwanted oxidation of a metal
Oxygen reduction:
O2(g) + 4H+(aq) + 4e- ® 2H2O(l)
Eo = 1.23V
@ pH 7, E = 0.82 V
Iron oxidation:
Fe(s) ® Fe2+(aq) + 2e- Eo = 0.44V
O2 free water
O2 in water
O2(g) + 4H+(aq) + 4e- ® 2H2O(l) Eo = 1.23V
@ pH 7, E = 0.82 V
2Fe(s) ® 2Fe2+(aq) + 4e- Eo = 0.44V
_____________________________________
1) 2 Fe(s) + O2(g) + 4H+(aq) ® 2Fe2+(aq) + 2H2O(l)
1/2 O2(g) + 2H+(aq) + 2e- ® H2O(l) @ pH 7, E = 0.82

V
2 Fe2+(aq) ® 2 Fe3+(aq) + 2e- Eo = -0.77V
_____________________________________
2) 2 Fe2+(aq) + 1/2O2(g) + 2H+(aq) ® 2Fe3+(aq) + H2O(l)
3) 4 H2O(l) + 2Fe3+(aq) ® 6 H+(aq) + Fe2O3 H2O(s)
Overall:
2 Fe(s) + 3/2 O2(g) + H2O(l) ® Fe2O3 H2O(s)
Preventing Corrosion
Use sacrificial anode:

Zn(s) ® Zn2+(aq) + 2 e- Eo = 0.76 V
More positive oxidation potential than
Fe(s) ® Fe2+(aq) + 2e- Eo = 0.44 V
Makes protective ZnO layer
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17) Redox Titrations
A 25.0 mL of unknown concentration of FeSO4 in acid is
titrated with 0.1327 M KMnO4. It takes 16.42 mL to reach
the equivalence point. What is the concentration of
FeSO4? The (unbalanced) net ionic equation is:
Fe2+ + MnO4- ® Mn2+ + Fe3+

Redox Titrations
A 25.0 mL of unknown concentration of FeSO4 in acid is
titrated with 0.1327 M KMnO4. It takes 16.42 mL to reach
the equivalence point. What is the concentration of
FeSO4? The (unbalanced) net ionic equation is:
Fe2+ + MnO4- ® Mn2+ + Fe3+

5Fe2+ + 8H+ + MnO4- ® Mn2+ +4H2O + 5Fe3+
! 0.1327molKMnO4 $! 1molMnO4− $! 5molFe 2+ $! 1molFeSO4 $! $
0.01642L # &# &# &# &# &
" L %" 1molKMnO4 %" 1molMnO4− %" 1molFe 2+ %" 0.025L %
0.436M
Permangante (MnO4-) is purple and Mn+2 is colorless, so how can

the equilvalence point be determined?
Topic 12 Kinetics
Introduction to Kinetics
1) Rate law
Determining from experimental data
2) Collision Theory
k=Ae^(Ea/RT)
3) Integrated rate laws
half-life
nuclear chemistry first order activity
4) Mechanisms
A Tale of 3 Reactions
H2(g) + I2(g) → 2 HI(g) H2(g) + Br2(g) → 2 HBr(g) H2(g) + Cl2(g) → 2 HCl(g)
Careful experiments, One might be tempted to The mechanism of this reaction
carried out over many suppose that this would is different again. Although the
years, are consistent with proceed in a similar way, . but first two reactions reach
the simplest imaginable experiments reveal that the equilibrium in minutes to an
mechanism: a collision mechanism of this reaction is hour or so at temperatures of
between the two far more complex. The 300 to 600 K, a mixture of
reactant molecules reaction takes place in a hydrogen and chlorine will not
results in a succession of steps, some of react at all in the dark, but if
rearrangement of the which involve atomic H and you shine a light on the
bonds: Br. mixture, it goes off with a bang
as the instantaneous reaction
releases heat and expands the
gas explosively.
Lower, S. Chem1 Virtual Textbook http://www.chem1.com/acad/webtext/dynamics/dynamics-1.html Accessed March 2012.

Thermodynamics ≠ Kinetics
Consider a generic reaction:
aA+bB⇌cC+dD
Thermodynamics: The reaction will progress until free
energy is minimized (it reaches equilibrium.) The
composition at equilibrium is predictable from data in
tables using the free energy of the reaction, its
stoichiometry, and the temperature.
c d
(ΔHº, ΔSº, ΔGº, ΔE )
o [C] [D]
K=
[A]a [B]b
Thermodynamics cannot relate how fast!

€
Kinetics…Rate of Reactions
Measure rates as changes in concentrations or pressures
over time
Ø Start with all reactants; no products
Ø Focus (mostly on) the forward reaction
Ø Average or instantaneous or initial???
Find rate law (relationship between the rate and the

concentrations of reactants) rate = k*[A]x
Break into simple steps (mechanism) to understand rate of

reaction
Cannot be predicted from stoichiometry, ΔHº , ΔSº, or ΔGº ;

experimental data must be collected
AàB
Average Rate
DB2
Δ[B] [B] final −[B]initial
=
Δt t final − tiniital
Dt
Reaction slows down;
DB1
rate varies DB >DB
1 2
Dt
Averill, B. Eldredge, P. General Chemistry Principles, Patterns, and Applications v 1.0, Flat World Education, Inc.
2014. (http://catalog.flatworldknowledge.com/bookhub/4309?e=averill_1.0-ch14_s02#) Accessed Nov. 21,
2014.
Initial Rate
Initial rate: the rate of the reaction under the starting conditions,
before the decrease in [reactants] and increase in [products]
significantly affects the rate
Formally, initial rate is the instantaneous rate when t = 0
In practice, initial rate is average rate from t = 0 to t = small
Instantaneous Rate
AàB
Δ[B]
instantaneous rate ∝
Δt
where Δt appoaches 0
The instantaneous rate is the rate at an exact point in time (the

tangent line drawn to the graph at that point)
Instantaneous rate depends on the time chosen
Finding the Rate Law
The rate law describes the relationship between the rate of the reaction and
the pressure or concentrations of the reactants.
Find x and y (orders) experimentally; they

A + 2B à are not necessarily the stoichiometric
x y coefficients.
rate = k[A] [B]
Zero-order reactions
k is the rate constant x = 0, y = 0
rate = k
Examples: isomerization, dissolving
First-order reactions
x = 1; y = 0 OR x = 0; y = 1
rate = k[A] or rate = k[B]
Examples: radioactive decay
Order of Reaction (cont’d)
Second-order reactions
A + 2B à (x = 1; y = 1) OR (x = 2; y = 0) OR (x = 0; y = 2)
x y
rate = k[A] [B] Rate = k[A]2 or k[A][B]
Examples: formation of diatomics
Overall reaction order

Sum of powers of all reactants in rate law
If rate = k[A]2[B]1, then:

Order in A = 2
Order in B = 1
Order for overall reaction = 3
Finding Orders Experimentally
Method 1: Graphing Rate Law
Zero-order reactions First-order reactions Second-order reactions
Rate = k Rate = k[A] Rate = k[A]2
Rate
Rate
Rate
[A] [A] [A]2

Finding orders experimentally: Instantaneous rates
*one experiment per reactant order
2 N2O5 → 4 NO2 + O2
Time P(N2O5) [N2O5] Rate x10-4

(min) (M) (M/min)
0 301.6 0.0152
10 224.8 0.0113 3.4
20 166.7 0.0084 2.5
30 123.2 0.0062 1.8
40 92.9 0.0046 1.3
69.1 69.1 0.0035 1.0
calculate Instantaneous rate

measure
from graph

Finding orders experimentally: Instantaneous rates
2 N2O5 → 4 NO2 + O2
Plot rate vs. [N2O5]2
rate = k[N2O5]
Plot rate vs. [N2O5]

Finding orders experimentally: initial rates
2 N2O5 → 4 NO2 + O2
Run a series of trials using five

different initial concentrations of
N2O5.
Use the tangents at the beginning

of each plot — that is, at time t=0
to determine initial rate.

Finding orders experimentally: Initial rates
2 N2O5 → 4 NO2 + O2
Graph rate law:

rate = k[N2O5]
slope = k
M −4
3.6x10
s −3 1
k= = 5.2x10
0.069M s
rate = (5.2 ×10-3 s-1) [N2O5]

Finding orders experimentally
One experiment (or series of experiments) per reactant where

other reactants are run in great excess
Example: A + B + C → products determine order in B
A B C
P 2 mol 0.02 mol 2 mol
U -0.02 -0.02 -0.02
G 1.98 0 1.98
Changes in A and C only 1% (This has minimal impact on

rate w/i experimental error)
Associate any impact on rate with [B] only

Finding orders experimentally: table of data
Problem 1: A+B→C
Trial Initial [A] Initial [B] Initial Rate
1 1M 1M 10 M/s
2 2M 1M 40 M/s
3 1M 2M 10 M/s
Finding orders experimentally: Table of data
A+B→C
1 1M 1M 10 M/s
2 2M 1M 40 M/s
3 1M 2M 10 M/s
For B: changing [B] doesn't change the rate in this

example, [B] has no effect and y = 0
rate = k[A]2[B]0 = k[A]2

Finding orders experimentally: Table of data
Determining a Rate Constant: k
A+B→C
1 1M 1M 10 M/s
2 2M 1M 40 M/s
3 1M 2M 10 M/s
We determined that rate = k[A]2
Now substitute in rate and [A], and solve for k
10 Ms
10 M
= k (1 M)
2
2
=k
s 1M
1
10 M•s = k
rate = (10 1/(M s))*[A]2
€
The Units of k
The units of k must cancel out in the rate law to give units of rate
(often rate will be M/s)
The units of k will depend on the order of the reaction:
"M% M mol
M =
rate$ ' = k k in s L•s
Zero-order: # s& s
"M% 1
rate$ ' = k[M] k in
First-order: # s& s €
€
"M%
Second-order: rate$ ' = k[M]2 k in
1
€ # s& Ms
n-order: "M% 1
€ rate $ ' = k[M]n in n −1
#s& M •s
€
Determine the rate law
The peroxydisulfate ion (S2O82−) is a potent oxidizing
agent that reacts rapidly with iodide ion in water:
S2O82−(aq) + 3I−(aq) → 2SO42−(aq) + I3−(aq)
Exp [S2O8-2] (M) [I-] (M) Initial rate (M/s)

1 0.27 0.38 2.05
2 0.40 0.38 3.06
3 0.10 0.22 0.44
Exp [S2O8-2] (M) [I-] (M) Initial rate (M/s)
1 0.27 0.38 2.05
2 0.40 0.38 3.06
3 0.10 0.22 0.44
Find Rate Law (show relationship between rate and [reactants])
rate = k[A] [B] x y

Find x and y (orders) experimentally; the
are not necessarily the stoichiometric
coefficients
Instantaneous or initial rates
zero order
rate
At least one experiment
rate
1st order 2nd order
per reactant [A] [A]2
Table of Initial rate data

Exp [A] [B] Initial
Need n+ 1 sets of data
Rate
where n is the number of
1 1M 1M Rate 1 components in the rate law
2 1.5M 1M Rate 2
3 2.0M 2M Rate 2
Find Rate Law (show relationship between rate and [reactants])
rate = k[A] [B] x y

Find x and y (orders) experimentally; the
are not necessarily the stoichiometric
coefficients
Instantaneous or initial rates
zero order
rate
At least one experiment
rate
1st order 2nd order
per reactant [A] [A]2
Table of Initial rate data

Exp [A] [B] Initial
Need n+ 1 sets of data
Rate
where n is the number of
1 1M 1M Rate 1 components in the rate law
2 1.5M 1M Rate 2
3 2.0M 2M Rate 2
What affects k?
Collision Theory (gas phase)
Reactions will take place if all three criteria are met.
1) Molecules collide
*In a gas @298K and 1bar, there will be ~ 1033 collisions per cm3/s
2) There is enough energy (Emin/activation energy)
3) The orientation is correct
CO(g) + O2(g) à CO2(g) + O(g)
Figure 1 [online image] Retrieved

November 15, 2016 from:
https://opentextbc.ca/chemistry/cha
pter/12-5-collision-theory/
How do I increase collision rate?
Increase the # of collisions
1) Increase concentration
2) Increase surface area
3) Stir
4) Increase temperature
Reactions go faster at
higher T:
food spoils faster
food cooks faster
Brown, W. P. Doc Brown’s Chemistry, “Factors affecting the speed-rates of chemical reactions.”
Accessed Nov, 2010. http://www.docbrown.info/page03/3_31rates.htm
Emin is Activation Energy
Activated complex (transition state)

-transient, highest energy point
Activation energy comes from:

-thermal energy
-absorption of light
-overpotential (in an
electrochemical reaction)

Activation Energy Plots
Exothermic Endothermic
medium Ea
high Ea 0 Ea

Arrhenius Law
−E A
k = Ae RT
The higher the T, the more
k – rate constant collisions and the more
Ea activation energy molecules with enough Ea.
R -gas constant (J/Kmol)
A-pre-exponential factor Boltzmann plot
(combination of frequency of
collisions and collision
orientation)
A and Ea are nearly independent of
T; depend on reaction

−E A
Arrhenius Law: k = Ae RT
Determining Activation Energy
Ea # 1 &
ln k = ln A − % (
R $T '
y= b + m x
€
Run experiments at several T;

measure k
T oC 1/T Ea
k s- ln k − = −3.27x10 4 K
(K-1 X10-3) R
477 1.33 0.00018 –8.62 Ea
= 3.217x10 4 K
523 1.25 0.0027 –5.92
J
8.314
Kmol
577 1.18 0.030 –3.51
kJ
E a = 273
623 1.11 0.26 –1.35 mol
Concept Question 2
The diagram below shows Arrhenius plots for
two first order chemical reactions. Which
reaction has the larger activation energy?
Ea # 1 & ln k B
ln k = ln A − % (
R $T '
1/T
Rate law −E A
Orders are determined experimentally by k = Ae RT

graphing the rate law or comparing tabular data
of initial rates k2 E a # 1 1 &
ln = % − (
k1 R $ T1 T2 '
rate = k[A]x[B]y
€
k is affected by temperature and by catalysts k1 E A2 − E A1
that lower activation energy
ln =
€ k2 RT
Rate constant k changes with Temperature
Ea
ln k1 = ln A − Subtract and
RT1 k2 E a # 1 1 &
rearrange ln = % − (
ln k 2 = ln A −
Ea k1 R $ T1 T2 '
RT2
Ea changes with Catalyst

1. € speed up a reaction but are not
Catalysts are substances that
consumed by it and do not appear in the net reaction equation.
2. Catalysts affect the forward and reverse rates equally.
3. Catalysts function by allowing the reaction to take place

through an alternative mechanism that requires a smaller
activation energy
Catalysts:
Alternative
mechanism
Lower, S. Chem1 Virtual Textbook

http://www.chem1.com/acad/webt
ext/dynamics/dynamics-1.html
Accessed March 2012.
Different catalyst; same reaction
H2O2 ® O2(g) + H2O(l) DGo = -210 kJ
catalyst Ea kJ/mol Relative rate
none 75 1
iodide 56 2140
Colloidal Pt 50 24,000
catalase 21 2,900,00
H2O2 + soap + KI http://www.youtube.com/watch?v=ezsur0L0L1c&feature=related
Homogeneous: same phase

Heterogeneous: different phase
Enzymes
http://www.chem1.com/acad/webtext/dynamics/catalyst-1.html
If a catalyst reduces the Ea of a reaction from
100 kJ/mol to 50 kJ/mol, how much faster will
it be at 298K?
−E A1
k1 Ae RT
(100
kJ
−50
kJ 1000J
)
= −EA 2 mol mol 1kJ
k2 # J &
Ae RT k1 E a 2 −E a 1
% 8.314 ((298K )
$ Kmol '
−E A1 =e RT
=e
k1 e RT
k2
= −EA 2
k2 k1
e RT
− E A1 E A 2
= e 20.18 = 5.8x10 8
k1
=e
RT
+
RT k2
k2
k1 E A2 − E A1
ln =
k2 RT
Rate law −E A
Orders are determined experimentally by k = Ae RT

graphing the rate law or comparing tabular data
of initial rates k2 E a # 1 1 &
ln = % − (
k1 R $ T1 T2 '
rate = k[A]x[B]y
€
k is affected by temperature and by catalysts k1 E A2 − E A1
that lower activation energy
ln =
€ k2 RT
Using rates and orders we can:

-predict a concentration at a give time Integrated rate law
-determine when a reaction will be “finished”
-predict impacts of changes in concentration Integrating
on the rate rate (of reaction) = rate law
-possibly disprove or support a mechanism allows us to do these more directly
Integrated Rate Laws
A®B
Zero order First order Second order

rate d[A] d[A]
d[A] = k[A]2
= rate law − =k − = k[A] −
dt dt dt
[A ]t t [A ]t d[A] t [A ]t−d[A] t
Integral ∫ [A ]o
d[A] = ∫ 0
−kdt ∫[A ]o [A] = ∫ 0 −kdt ∫[A ]o [A]2 = ∫ 0
kdt
€ € €
[A]t − [A]0 €
= −kt
" [A]t % 1 1
Integrated
€ ln$ ' =€−kt − = kt
rate law # [A]0 & [A]t [A]0
[A]t = −kt + [A]0 [A]t = [A]0 e−kt [A]0

Solve€for [A]t [A]t =
€ 1+ [A]0 kt
€
Determine order by integrated rate law graphs
Zero order First order Second order
1 1
[A]t = −kt + [A]0 ln[A]t = −kt +ln[A]0 = + kt
[A]t [A]0
y = mx + b y = mx + b y = b + mx
€ 1
€
Graph [A]t vs. t ln[A]t vs.
€ t vs t
[A]t
€ € €
€
€
€
Slope = -k -k k
No need to measure/calculate rate; instead us [ ] and time

Lines verify order
Plot rate laws
zero order
rate rate Martin Hanford and Wall (Waldo) and
related characters. From
1st order 2nd order https://en.wikipedia.org/wiki/Where%
27s_Wally%3F#/media/File:MartinHan
dfordWally%26Friends.PNG April 5,
2017.
[A] [A]2
One experiment per
reactant with others
run in excess
Plot integrated rate laws
Measure Calculate zero order 1st order 2nd order
time [A] ln[A] 1/[A] [A]t ln[A]t 1/[At]

0
1 t t t
2.. ln[A]t = ln[A]o − kt
1 1
[A]t = [A]o − kt =
[A]t [A]o
+ kt
Problem 1
To prepare a 15 kg dog for surgery, 150 mg of the anesthetic
phenobarbitol is administered intravenously. The reaction in
which the anesthetic is metabolized is first order in phenobarbitol
and has a half-life of 4.5 h. After 2 hours, the drug begins to lose
its effects. However, the surgical procedure requires more time
than had been anticipated. What mass of phenobarbitol must be
re-injected to restore the original level of anesthetic to the dog?
Half-Life: First Order way to convey k
The half-life (t½) of a reaction is the time it takes for a reactant to
reach half of its original concentration
To derive the equation, solve the integrated raw laws for t when
[A]t = ½[A]0
" [A]t %
ln$ ' = −kt
# [A]0 &
"1 %
$ 2 [A]0 '
ln$ ' = −kt1/ 2
$ [A]0 '
# &
−ln(1/2) ln2
= = t1/ 2
k k
For first order reactions (only)
t1/2 is independent of initial concentration!
Problem 1
To prepare a 15 kg dog for surgery, 150 mg of the anesthetic
phenobarbitol is administered intravenously. The reaction in
which the anesthetic is metabolized is first order in phenobarbitol
and has a half-life of 4.5 h. After 2 hours, the drug begins to lose
its effects. However, the surgical procedure requires more time
than had been anticipated. What mass of phenobarbitol must be
re-injected to restore the original level of anesthetic to the dog?
Ao = 150mg
At = Aoe−kt
ln2
t1/ 2 = 4.5h = 1
(−0.15 )(2h )
k = 150e h
1
0.15 = k = 110.2
h
t = 2h add39.8mg
Half-life: zero and second order
Zero order Second order
1 1
[A]t = −kt + [A]o − = kt
[A]t [A]o
1
sub in [A]t = [A]o 1
2 sub in [A]t = [A]o
2
1 1 1
[A]o = −kt1/ 2 + [A]o − = kt1/ 2
2 1 [A]
1 [A]o o
− [A]o = −kt1/ 2 2
2 1
= kt1/ 2
1[A]o [A]o
= t1/ 2
2k 1
= t1/ 2
k[A]o
Kinetics of Nuclear Decay
The general reaction is: A1 X → A2 Z2Y + ”radioactivity”
Z1
Nuclear decay is always first order, so rate = k[X] or

Activity(rate) = kN
Nt = N0e-kt t½ = ln2
k is decay constant k
N is # atoms in sample
Activity (rate): # disintegrations per time

Bq (bacquerel) = 1 disintegration/s
Ci (curie) = 3.7x1010 Bq
Uranium-238 decay series
Times are 1/2 lives of

nuclides
(a = year)
Decay of Uranium-238 [online image]. Retrieved November 15,

2016 from: http://metadata.berkeley.edu/nuclear-
forensics/Decay%20Chains.html
Problem 2
90Sr is a radioactive by-product of nuclear reactors that behaves biologically
like calcium. When 90Sr is ingested by mammals, it is found in their milk and
eventually in the bones of those drinking the milk. A sample of 90Sr, has an
activity of 1.2x1012 Bq, what are the activity after 59 a?
t½ 90Sr = 29 a.
Problem 2
A sample of 90Sr, has an activity of 1.2x1012 Bq, what is the activity after 59
a? t½ 90Sr = 29 a.
Find k
Ao = kN o Find No
ln 2 ln 2 1
k= = = 2.39x10 −2 dis 1 1a 1d 1h
t1/2 29a a 1.2x1012 = 2.39x10 −2 * * * No
s a 365.25d 24h 3600s
Use activities in 1st order 1.58x10 21 = N o
equation
N t = N o e−kt Use No to Find Nt
−kt
At kN t kN o e
= = 1
−2.39 x10−2 (59a)
Ao kN o kN o = 1.58x10 e 21 a
At N t = 3.86x10 20
= e−kt
Ao
Use Nt to find At
−2 1 A t = kN t
At −2.39 x10 (59a)
12
=e a 1
= 2.39x10 −2 * 3.87x10 20 *
1a
*
1d
*
1h
1.2x10 a 365.25d 24h 3600s
dis
At = 2.93x1011 = 2.93x1011
s
11
= 2.93x10 Bq
Radioactive (Radiometric) Dating
Radioactive dating: the process of using radioactive isotopes to
determine the age of an object.
6C is formed by reaction of 14N in the atmosphere:

14
14 N + 1 n ® 14 C + 1 p
7 0 6 1
6C
has a half-life of ~5700 years, and is taken up by living
14
organisms (equivalent to 126C in chemical reactions)

Once organisms die, the number of 146C nuclei is set; no more can
be incorporated. After death, the number of 146C steadily
decreases.
Dating human artifacts based on plant/animal matter, up to

about 50,000 years ago
Problem 3
The charred bones of a sloth in a cave in Chile represent the earliest
evidence of human presence at the southern tip of South America. A
sample of bone has a specific activity of 5.22 dis/min per g of C. If the
ratio of 12C:14C in living organisms results in a specific activity of 15.3
dis/min per g, how old are the bones? (t½ 14C = 5730 a)
Problem 3
The charred bones of a sloth in a cave in Chile represent the earliest
evidence of human presence at the southern tip of South America. A
sample of bone has a specific activity of 5.22 dis/min per g of C. If the
ratio of 12C:14C in living organisms results in a specific activity of 15.3
dis/min per g, how old are the bones? (t½ 14C = 5730 a)
ln2 At
t1/ 2 = = e−kt
k Ao
ln2 d
5730a = 5.22
k min g
1
−1.21x10 −4 t
1 =e a
k = 1.21x10 −4 d
15.3
a min g
8887a = t
Mechanisms: Break a reaction down into a
series of elementary reactions
Cl×(g) + N3(g) ® ClN×(g) + N2(g)

Each step is elementary
ClN×(g) + N3(g) ® 2 N2(g) + Cl×(g)
2N3(g) ® 3N2(g)
Overall reaction
Catalyst goes into reaction and comes back out

Intermediate is formed and used up
Elementary Reactions
An elementary reaction describes a simple collision or dissociation.
Elementary reactions can be:

Unimolecular A ® rate = k[A] k is the rate constant
Bimolecular A + A ® rate = k[A][A] *same k as from Arrhenius
or A + B ® rate = k[A][B]
Termolecular A + A + A ® rate = k[A][A][A]
or A + A + B ® rate = k[A][A][B]
or A + B + C ® rate = k [A][B][C]
Very rare
The stoichiometric coefficients of an elementary reaction
relate the concentrations/pressures of the reactants to
the rate of the reaction. This relationship is knows as the
rate law.
Mechanism
A mechanism breaks an overall reaction into a series
of elementary steps.
2A + 2B ® C (overall reaction)
Proposed Mechanism
k
1) A + B ® Q
1
k
2) Q + A ® R2
k 3
3) R + B ® C
Each step has a different k
Reaction steps are often
designated "fast" or "slow"
based on the rate constant (k)
small k is slow
1) A + B ® Q (slow, rate-determine)
2) Q + A ® R (fast)
3) R + B ® C (fast)
When the k’s are different, the

slow step becomes rate-
determining
Rate-determining step. [online image]. Retrieved November 15, 2016 from
http://chem.libretexts.org/Textbook_Maps/General_Chemistry_Textbook
_Maps/Map%3A_Chemistry%3A_The_Central_Science_(Brown_et_al.)/14
large k is fast %3A_Chemical_Kinetics/14.6%3A_Reaction_Mechanisms
The Rate-determining step
Overall activation energy = Ea (red line to left)

Rate determining step has the highest transition state (step 3)
http://www.youtube.com/watch?v=HnbNcQlzV-4
Problem 1:
a) How many steps does this reaction have?

b) Which is the rate-determining (slow) step?
c) Which step is fastest?
d) How many intermediates form in the reaction?
Do any of intermediates build up in concentration?
e) A catalyst is added that accelerates the third step only. What
effect, if any, will the catalyst have on the overall rate of
reaction?
Mechanism: (slow first step)
Proposed Mechanism
k
1) A + B ® Q (slow, rate = k1[A][B]
1
k
2) Q + A ® R (fast)
2
Q is consumed as quickly as it
k is formed; its rate of formation
3) R + B ® C (fast)
3
is rate determining.
2A + 2B ® C (overall reaction)
overall rate = rate of formation of Q = k1[A][B]
Mechanism:
(2nd step is slow, preceded by a very fast step)
O3(g) ® O2(g) + O(g) Rate = k1[O3] v. fast
O3(g) + O(g) ® 2 O2(g) Rate = k2[O3][O] slow
sub in for intermediates as much as possible

(OK to have H+ and OH- in aqueous solutions)
Mechanism:
(2nd step is slow, preceded by a very fast step)
O3(g) ® O2(g) + O(g) Rate = k1[O3] v. fast
O3(g) + O(g) ® 2 O2(g) Rate = k2[O3][O] slow
sub in for intermediates as much as possible

(OK to have H+ and OH- in aqueous solutions)
[O] = k1[O3] - k2[O3][O] Rate = k2[O3]k1[O3]

**assumption k1[O3] >> k2[O3][O] = k2k1[O3]2
[O] = k1[O3]
=k[O3]2
***The rate of formation of [O] is so much faster than the rate it is

consumed that the rate of consumption of [O] is insignificant.
Mechanism: (Fast pre-equilibrium)
k1 k-1
*Assume a fast step
1) Cl2 Û 2 Cl (fast equilibrium K1) after a slow
k2 k-2 equilibrium makes it
2) Cl + CO Û ClCO (slow equilibrium K2)* one-directional
k3
3) ClCO + Cl2 à Cl2CO + Cl (fast)
k4
4) 2 Cl à Cl2 (fast)
Mechanism: (Fast pre-equilibrium)
k1 k-1
*Assume a fast step
1) Cl2 Û 2 Cl (fast equilibrium K1) after a slow
k2 k-2 equilibrium makes it
2) Cl + CO Û ClCO (slow equilibrium K2)* one-directional
k3
3) ClCO + Cl2 à Cl2CO + Cl (fast)
k4
4) 2 Cl à Cl2 (fast) Assume [Cl] is determined by fast
step 1; step 2 is slow so it doesn’t
change the [Cl] by consuming it.
rate = k2 [Cl][CO].....from slow
Sub in for intermediate Cl From step 1
@equilibrium rate fwd = rate rev
rate = k2 ( )
K1[Cl2 ] [CO]
k1[Cl2 ] = k−1[Cl]2
1
rate = k[Cl2 ] 2 [CO] k1 [Cl]2
= = K1
k−1 [Cl2 ]
k = k2 K11/2 [Cl] = K1[Cl2 ]

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Topic 1: Gases

6. vrms (Boltzman distribution) MW 3RT

7. Mixtures of gases P = X P = n RT P = P + P +...

The American Heritage Dictionary of the English Language. The Free

-in constant motion

force (F) mass * acceleration mass(m) * gravity(g)

Why do hammers have small heads?

Atkins, Nolan, Updated 8/25/08

1 bar = 1.00 x 105 Pa = 100 kPa

1 atm = 760 mm Hg* = 760 torr

*mm Hg is pressure exerted by a column of mercury at 15oC in a standard

1 atm = 14.7 lb/in2 (psi)

There is an equal pushing

Glogster-Poster Yourself. “kinetic molecular theory.” Updated November 2009.

What causes an€

Glogster-Poster Yourself. “kinetic molecular theory.” Updated November 2009.

What causes an€

Smaller volume (V)

Lower, S. (2010) Retrieved September 6, 2016 from: http://www.chem1.com/acad/webtext/gas/gas_2.html

-273.15 °C is absolute zero

1) Density 3) Graham’s Law

And when it doesn’t….

HCl(g) air NH3(g)

Diffusion can also occur in liquids

Retrieved September 6, 2016 from

At constant temperature, the rate of effusion (or diffusion) of a gas

Use same conditions; compare times for same # of moles effused

Derivation see: http://www.chem1.com/acad/webtext/gas/gas_5.html

Asymmetric, with no theoretical upper limit

Higher vrms; higher rate effusion

Higher vrms @ higher T

Higher temperature, broader distribution, higher speed

Higher MW, narrower distribution, lower vrms https://www.youtube.com/wa

1 molecule N2 at 20oC and 1 bar

vrms = 510 m/s (1100 mi/h)

Mean free path Collisions every 6.6x10-8 m

Molar Volume Vm : the volume (of a flexible container)

-these particles move in a straight line until they collide with

-collisions between gas particles or the sides of the container

-*most of the volume of a gas is empty space; gas molecules

-*there is NO force of attraction (IMF) between gas particles or

For ideal gases, Z = 1

400 atm divide

IMF kJ/m note

Figure 5.29 CHEMICAL PRINCIPLES|ATKINS|JONES|LAVERMAN ©2013

This correction does not account for

Ideal Reality Check

3. The first law of thermodynamics Change in T?

Internal energy (U): Sum of kinetic and potential energies

Law of conservation of energy: total quantity remains

The internal energy (U) of an isolated system is constant.

U = ( Σ(KE1 + KE2 +....)) +( Σ(PE1 + PE2 +....))

Work and heat are pathways for adding/taking

Work (w) and heat (q) are pathways for adding/taking

system gains energy system loses energy

Heat in Heat out

ΣKE1 + KE2 + KE3 +.....

U = ( Σ(KE1 + KE2 +....)) +( Σ(PE1 + PE2 +....))

expansion -PexDV Pam3 = (kg/ms2)m3= J

Raising weight mgDh kg(m/s2)m=J

electrical DEq VC=J