Assignment

Chapter 5 Problems: ONE COLLECTED TODAY

1,2,7,9,11,14,17,19,21,24,26,28,30,33,37,42,43,44,48,
49,51,53,55,57,62,63.

REVIEW & PROBLEM SOLVING Tonight C-109 5PM

Exam 2----Friday, August 24.

--Coverage from end of Chapter 3 to page 236.

Skip pages -205-209--no calculations involving non-

ideal gases just conceptual.
 Only heat and work can change internal energy.

Surroundings
+q = heat Internal Energy -q = heat lost
from the
added
System
system
+w = work
-w = work
done on Rotation, Vibrations,
Electronic, done by the
the system
translational energies system

Surroundings
 First Law of Thermodynamics
• A system contains only internal energy.
– A system does not contain heat or work.
– These only occur during a change in the system.
Heat Work

!E = q + w
• 1st Law of Thermodynamics: Conservation of Energy
– In interactions between a system and its surroundings the total
energy remains constant— energy is neither created nor
destroyed just transformed between the two.

!Esystem + !Esurroundings = 0
 Subtle But Key Points
• There are only two ways that a system
exchanges energy with its surroundings: (1)
heat transfer (q) 2) by work (w).

• There is no “absolute heat” there must be a

change in the system.

q
Surroundings
System w
!Esys = q + w
 PV = Energy = Work
PV has units of energy we call it WORK

101.3 J = 1 L atm

w = P × ∆V

height

w = F orce × Distance
F orce Area
w= × height
Area
w = P × (Area × height)
w = P × ∆V
 Watch the Units of Work
q
Surroundings
System w
Note that: 101.3 J = 1 L atm

!Esys = q + w
w = -P!V
!Esys = q - P!V
!Esys = q - P(Vf - Vi)
 PV-Work Example
• Calculate the work (in kilojoules) done during a
reaction in which the volume expands from 12.0 L to
14.5 L against an external pressure of 5.0 atm.
Watch the conversion of PV units to joules.

P = 5.0 atm !V = (14.5-12.0) L = 2.5 L

w = –P!V
w = -(5.0 atm)(2.5 L) = -12.5 L·atm
(-12.5 L·atm)(101 J/L·atm) = -1.3 " 103 J = -1.3 kJ
 The Key Riff

Any thermodynamic system in an equilibrium state posses a state

function called internal energy. Between any two states the
change in internal energy that takes place is equal to the
difference in heat transfer into or from the system and the work
done by or on the system (energy changes because of heat and
work only!)
 State Functions Don’t Depend On Path
A state function is a function that only depends on the initial
and final states and not how the path taken to between the two
states.
All state functions!
PE = mgh
!E = Efinal - Einitial
!P = Pfinal - Pinitial
h !V = Vfinal - Vinitial
!T = Tfinal - Tinitial

!H = Hfinal - Hinitial
Potential energy of hiker 1 and hiker 2
is the same even though they took
different paths.
Temperature is a state function, it does not depend whether we
start with boiling water at 100˚C or frozen water at 0˚C. Once
we get to 50˚ the difference in temperature is 50˚C.
Internal Energy Changes In Chemical Reactions
Determining the Change in Internal Energy of a System

PROBLEM:

When gasoline burns in a car engine, the heat released

causes the products CO2 and H2O to expand, which
pushes the pistons outward. Excess heat is removed by
the car’s cooling system. If the expanding gases do 451 J
of work on the pistons and the system loses 325 J to the
surroundings as heat, calculate the change in energy (!E)
in J, kJ, and kcal.
PROBLEM:
When gasoline burns in a car engine cylinder, heat
released causes the products CO2 and H2O to expand,
which pushes the pistons outward. Excess heat is
removed by the car’s cooling system. If the expanding
gases do 451 J of work on the pistons and the system
loses 325 J to the surroundings as heat, calculate the
change in internal energy (!E) in J, kJ, and kcal.

PLAN: Define system and surroundings, assign signs to q and w

and calculate !E. The answer should be converted from J
to kJ and then to kcal.
SOLUTION:
q = - 325 J w = - 451 J

!E = q + w = -325 J + (-451 J) = -776 J

kJ kcal
-776J = -0.776kJ -0.776kJ = -0.185 kcal
103J 4.18kJ
Chemists don’t use internal energy as a
yardstick in monitoring energy changes
in chemical reactions.

We use its cousin and give it a di!erent

name: ENTHALPY
Let’s Play With The Internal Energy Equation

!E = q - P!V
CASE 1 CASE 2
At constant pressure: At constant volume: !V=0

!E = qP - P!V !E = qV - P!V
qP = !E + P!V !E = qV

Enthalpy = !H = qP = !E + P!V
Chemical Reactions will either give off heat or
absorb heat from the surroundings. The energy
changes are state functions and normally carried
out at constant pressure.

We use ENTHALPY as the yardstick or ruler to

quantify and communicate the heat given off or the
heat absorbed!

H2O (s) "# H2O (l) !H = 6.01 kJ/mol

That’s called a
thermochemical equation---
with the !H it tells us
something about heat that
is absorbed or given off by
the chemical reaction
Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the surroundings.

2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

• An exothermic reaction gives off thermal energy = heat = q

Endothermic process is any process in which heat has to be

supplied to the system from the surroundings.

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

• An endothermic reaction feels cold.
 Enthalpy is very close to internal energy

Enthalpy = !H = qP = !E + P!V

I. In solids and liquids there is no volume change

(or it is small) then P!V = 0 and !H = !E

II. Reactions in which the number of moles of gas

does not change. N2 + O2 ----> 2NO

III. Reactions in which the number of moles of gas

does change but q is >>> P!V.
A Comparison of !H and !E

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) !H = -367.5 kJ/mol

!E = !H - P!V At 25˚C, 1 mole H2 = 24.5 L at 1 atm

P!V = 1 atm x 24.5 L = 2.5 kJ

!E = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol
!H and It’s Applications In Chemistry
Enthalpies That We Measure In the Lab

!H = qP = !E + P!V
Heat Transfer continues to equilibrium

Heat transferred = q $ !T

q = C !T
C = heat capacity
Heat Capacity Is Intensive Property of Matter

Heat transferred = q $ !T (!T = Tfinal - Tinitial)

q = C !T
C is a material dependent constant called the Heat Capacity
units of Energy per degree T (J/°C, J/K, cal/°C, cal/K)

Units of s:
C = q / !T J /°C, J/ K

Heat capacity (C) of a substance is the amount of heat (q)

required to raise the temperature of a given quantity (m) of
the substance by one degree Celsius or Kelvin.
 Physics of Heat Transfer

C = q / !T

We also find that heat capacity, C, of a material is

proportional to mass of a substance under question. We can
write:

C m

where m is mass and

C=m s
Units of s: s is a constant called
J/g °C, J/g K the specific heat
capacity
 Specific Heat (Capacity), s
The specific heat (s) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
substance by one degree Celsius.

C=m s
Units of s:
(1)
J/g °C, J/g K

q = C !T (2)

Substituting specific heat (1) for heat

capacity C in equation 2 gives:

Heat (q) absorbed or released:

q = s m !T
Calculating Specific Heat Capacity
How much heat is required to raise the temperature of
1.0 x 103 kg of iron from 25 °C to 75 °C if the specific
heat capacity of iron is 0.45 J/g °C?

Heat (q) absorbed or released:

q = s m !T