Do Problem 40 in Chapter 1

Pid = RT/Vm Vm,id = RT/P

Pvdw = RT/(Vm – b) – a/Vm2

Add Vid into VdW equation.

Adjust Vm to change P value until target P reached.

Have class do handout

Assign problem 20 and 35 for Friday

 What is the composition of the Universe?

Thermodynamics – The study of the interactions

between matter and energy.

The Laws of Thermodynamics

1. Conservation of Energy
or … “You can’t Win”

2. The Entropy of the Universe is Increasing

or … “You can’t break even”

3. A Pure Substance has 0 Entropy at 0K

Matter & energy
Isothermal (T)
Surroundings
Isobaric (P)

energy Open Isochoric (V)

System

adiabatic
no heat transfer

Closed
System isolated
system
 ENERGY OF SYSTEM
E = K + V + U

kinetic energy (½mv2) internal energy

potential energy
depends on the force field applied to the
system. E.g. gravity, electrostatic, etc.

U = Utr + Uvib + Urot + Uel + Uint + Unuc

Assuming K and V are not changing …… D E =

DU
 Thermodynamic Properties
Intensive Extensive
P isobaric n
T isothermal V isochoric
V/n or Vm U
U/n = Um, etc H, S, G
 The 1st Law of Thermodynamics
Conservation of Energy – The energy of the universe is constant.
The energy of a system can change if an equal amount of energy is transferred
to/from the surroundings in the form of heat or work.
For a given change in U, the values
DU = q + w of q and w will depend on how the
process is carried out; q & w are not
state functions.
heat (q) work (w)

State Function
A property of a system that is indicative of the state of the system
at the current time. P, V, T, U, H, G, S

Change of State – DT, DU, DP, etc. ….

The values of DT, DU, etc. are independent of path.

Equation of State – PV = nRT; G = H –TS;

indicates the relationship between the values of various state functions with
respect to other state functions
 Work (w)

work = force applied over a distance

extension work dw = Fx dx and w = ∫ Fx dx

gravitational work F = ma = mg (constant)

dw = mg dh or w = mgh

electrical work w = EIt Time (t) s

Volts (E) WA-1 or J s-1 A-1 current (I) Ampere (A)

 Work derivations
dw = Fx dx …..
w =  dw =  Fx dx if Fx is cst …

= Fx (x2 - x1) 2.1

dw = Fx dx: for gas P = F/A (area) & F = PA

dw = PA dx = P  Adx = P dV
dw = - P dV (- due to sign convention)
expansion w is (-) compression w is (+)
PV (expansion) work
system must allow for DV.

P = F/A & Fx = PA
 PV (expansion) work
system must allow for DV.

Fx = PA

w = - Fx dx = - PA dx = -  P dV
Reversible vs. Irreversible
Pext = Pf = constant
Reversible vs. Irreversible
Pext is not constant
250000
Work for reversible,
isothermal, IG expansion w = -  P dV =
n = 1.00 -  nRT dV/V =
200000
-nRT ln (V2/V1)

150000

PV Isotherm
P (Pa)
100000

50000
w = -RT ln (2) = -1729 J

0
0.01 0.012 0.014 0.016 0.018 0.02 0.022 0.024 0.026

V (m3)
 250000 Work for irreversible,
isothermal, IG expansion
n = 1.00 w = -  P dV
200000
= - P  dV
= -P (V2 – V1)
150000

P (Pa)
100000

50000
w = -P (V2 - V1) = -1247 J
0
0.01 0.012 0.014 0.016 0.018 0.02 0.022 0.024 0.026

V (m3) 2.4
 Solid/liquid volume changes are small compared to gas therefore work is much less.

Work - Solid/liquid examples

w = - ∫ P dV applies universally – not just to gases

however, do not try to substitute P = nRT/V for solids/liquids!

Work done during phase changes

(e.g. - side walk cracks from Duluth winters) See water data on page 37

How much work is done when 18.0 g of water freezes at 0 ºC?

density: ice = 0.915 g ml-1, water = 0.9999 g ml-1
W = -0.17 J
V (m3) = 1/(g ml-1) • 1 x 10-6 m3/cm3 • #g

Vm (m3) = 1/(g ml-1) • 1 x 10-6 m3/cm3 • FW g/mol

How much work is done heating 18.0 g of water from 0→100 ºC?
density: water (0ºC) = 0.9999 g ml-1, water (100ºC) = 0.9585 g ml-1
W = 0.079 J
Special case – Expansion into a vacuum
an irreversible process

What is Pext?

What is w?
w = -P • (V2 – V1) = 0

Assign 2.14 and 2.16

 Heat (q)
A measure of thermal energy transfer that can be measured
by the change in T of the system.

q = m1c1(Th -Tf) = m2c2(Tf -Tc)

q
T
Tf T
Tf
c h

c = specific heat: e.g. cal g-1 oC-1

 Heat Capacity
CP = dqP/dT (J K-1) or CP,m (J K-1 mol-1)
CV = dqV/dT (J K-1) or CV,m (J K-1 mol-1)

substance CP (J mol-1 K-1)

Cu 24.4
H2O 75.9
Fe 24.8
Pb 32.9
Cg 8.5
Cd 6.2
What would make the most efficient frying pan?

How much heat does it take to raise a 10carat diamond (1 carat = 0.2 g)
from 298K – 500K?
Isothermal change of state for an ideal gas
T causes these motions so if DT = 0 they don’t contribute to DU

0 for IG 0 for chemical process

D U = D Utr + D Uvib + D Urot + D Uel + D Uint + D Unuc

0 if no l absorption and D T =
0
DU = 0 any isoT, IG process
q = DU – w =
-w
Isothermal change of state for an ideal gas
T causes these motions so if DT = 0 they don’t contribute to DU

0 for IG 0 for chemical process

D U = D Utr + D Uvib + D Urot + D Uel + D Uint + D Unuc

0 if no l absorption and D T =
0
DU = 0 any isoT, IG process
q = DU – w =
-w
 Heat Capacity - CV,m and D U

CV,m = dqv/dT J K-1mol-1

From DUsys = q + w ……. Derive DU = qV

assume that only expansion work is possible
assume constant volume
DU = qV (constant V heat)
Sub in dU for dq in CV,m expression: CV = (dU/dT)V
Multiply both sides by dT: dU = CV dT
Integrate both sides: ∫dU = D U = ∫CV
dT CV is constant over T:
Assume
D U = CV ∫dT = CV (T2 – T1) = CV D T
This is independent of how the process is carried out.
 Equipartition Theorem (CM)
For a collection of particles at thermal equilibrium
the average contribution of each ‘degree of freedom’
to the total energy is 1/2kT.

Accurate for translation, Very good for rotations,

Poor for vibrations.
Utr contributes 3/2kT toward U for IG (per particle)
since 3 dimensions of motion

Utr contributes 3/2 RT toward Um for IG (dU/dT) = CV,m = 3/2 R

Monatomic IG (no rotations/vibrations) e.g. He, Ne, Ar…

CV,m = 1.5R = 12.47 J mol-1 K-1
 Enthalpy (H)
Begin with 1st Law DU = q + w (or dU = dq + dw)
cst P and expansion work only

By definition H = U + PV or dH = dU + d(PV)

dH = dqP – P dV + P dV + V dP = dqP
DH = qP U is cst V heat (qV) while H is cst P heat (qP)

CP = dqP/dT = (dH/dT)P and dH = CP dT

D H =  dH =  CP dT = CP
DT
if CP is independent of T
If CP,m = f(T) = a + bT + c/T2 then DH = qP =  CP dT ….

=  (a + bT + c/T2) dT
 Calculating q, w, DH and DU?
Properties of Water melting vs. boiling (n = 1)

Specific CP,m DH Density Density Volume

heat J K-1 mol-1 J mol-1 g cm-3 kg m-3 m3 mol-1
Jg K
-1 -1

ice 2.113 38.07 0.915 915 1.97 x 10-5

Fusion  6007
melting
Water 4.18 75.4 0.9999 999.9 1.80 x 10-5
0C
Water 4.18 75.4 0.9584 958.4 1.88 x 10-5
100C
Boiling  40,660
condensation

gas 1.874 33.76 5.88 x 10-4 0.588 0.0306

Is melting/boiling a Cst V or Cst P process? How can we calculate DU?

What are easiest variable(s) to determine from given data?
How can we calculate work? w = -P (V2 – V1)
 How different are DH and DU?
Solids or Liquids
H = U + PV & dH = dU + d(PV)
since solids/liquids are not very compressible
D (PV) ~ 0 (very small) & DH  DU

Ideal Gas
H = U + PV & PV = nRT
show DH = DU + Dn(g)RT
 Calculations
Find q, w, DU, and DH for …….
Isobaric heating/cooling of solids, liquids, or gases
data needed: CP,m (or CV,m for gases) and density

Phase changes -
data needed: D Htr - density

IG changes of state with specified conditions ….

isothermal (reversible/irreversible)
adiabatic (reversible)
Starting Points for w, q, DU, & DH calculations
Regardless of condition ….

Work w = -  P dV
Internal energy DU =  CV dT
DU = q + w

enthalpy DH = DU + D(PV)

DH =  CP dT
CP,m = CV,m + R (ideal gas)
w = -  P dV DU =  CV dT DU = q + w
DH =  CP dT
2.14
Gas – V1 = 377 ml to V2 = 119 ml with constant P = 1550 torr while removing 124.0 J of heat.
 
DU = q + w q = -124.0 P (Pa) = 1550/760 • 101325 = 2.07 x 105
w = -∫ P dV = - P (V2 – V1) = - 2.07 x 105 (0.000119 – 0.000377) = + 53.4 J
 DU = 53.4 – 124.0 = -70.6 J

What is DH?

DH = DU + P • DV
-70.6 1550/760 • 101325 -0.000258

= -124 = qP.
w = -  P dV DU =  CV dT DU = q + w
DH =  CP dT DH = DU + D(PV)
 
2.16 IG n = 1.000 mol V1 = 1.0 L to V2 = 10.0 L T = 298K
 
a. reversibly b. irreversibly against cst P = 1.00 atm
 
w = -∫ P dV = - nRT ln(V2/V1) = -1.000 • 8.314 • 298 • ln(10): wrev = -5700 J
 
w = -∫ P dV = - P (V2 – V1) = -101325 • (0.010 – 0.0010): wirr = -912 J
 
You get more work output when the expansion is done reversibly. 
Calculate DH, DU, and q for each part above?

DH = 0 , DU = 0, and q = +5700 J (reversible)

q = +912 J (irreversible)
w = -  P dV DU =  CV dT DU = q + w
DH =  CP dT DH = DU + D(PV)
Note that CP,m - CV,m = R
 2.16 IG n = 1.000 mol V1 = 1.0 L to V2 = 10.0 L T = 298K
 
a. reversibly b. irreversibly against cst P = 1.00 atm
 
w = -∫ P dV = - nRT ln(V2/V1) = -1.000 • 8.314 • 298 • ln(10): wrev = -5700 J
 
w = -∫ P dV = - P (V2 – V1) = -101325 • (0.010 – 0.0010): wirr = -912 J
For n = 1, V = 0.00100 m3, T = 298 K — gas is He with CV,m = 12.5 J mol-1 K-1

Gas is heated at constant volume to 400K.

Using IG law and equations above…. Calculate P1 and P2, w, DU and DH

P1 = 2.48 x 106 Pa P2 = 3.33 x 106 Pa w =0 DU = 1272 J

What is CP,m? = 20.8 J mol-1 K-1. DH = 2122 J
 Reversible, Adiabatic IG Process
q=0 w = D U = -  PdV =  CVdT
note that P, V, & T are all changing.
Equate above two expressions & solve to get ......
-  RT/Vm dV =  CV,m dT ln (V1/V2)R/Cv,m = ln (T2/T1)
- R  dV/Vm = CV,m  dT/T (V1/V2)R/Cv,m = T2/T1
- R/CV,m ln(V2/V1) = ln(T2/T1)

T2/T1 = (V1/V2)R/Cv,m or P1V1 g = P2V2 g (g = CP,m/CV,m)

DH = DU + D(PV)
 PV graph T2/T1 = (V1/V2)R/Cv
250000
1 mole of an IG at P = 2.00 bar and T = 300. K is expanded adiabatically
to a final volume of 0.0250 m3. What is w, q, DU, and DH.

200000 CV.m = 15.0 J mol-1 K-1

150000
isothermal
P (Pa)
100000

adiabatic
50000
T↓

0
0.01 0.012 0.014 0.016 V (m3)
0.018 0.02 0.022 0.024 0.026
 CP,m – CV,m = R for an ideal gas (proof)
Define: D H = n CP,m D T , D U = n CV,m D T
let n = 1, rearrange & sub into above
CP,m – CV,m = (D H/D T) - (D U/D T)
substitute D H = D U + D (PV)
= {DU + (D(PV)}/DT) - (DU/DT)
sub D (PV) = R DT (for n = 1)
= (DU + R DT - DU)/DT)
 
CP,m – CV,m =R
Internal Pressure

CP - CV = [(dU/dV)T + P] (dV/dT)P
 Joule Experiment:
measure DT as gas expands into vacuum: mJ = (dT/dV)U
find (dU/dV)T for real gas

Adiabatic Walls ― q = 0

but w = 0 also since Pext = 0

(dT/dU)V(dU/dV)T(dV/dT)U = -1 & (dU/dV)T = -mJCV
Result: DT was too small to measure with Joule’s apparatus
Joule-Thomson Experiment: (dT/dP)H = mJT

Adiabatic Walls: Measure T change

P1 P1 P1, V1 P2, V2 P2 P2
T1 T2

(dT/dH)P(dH/dP)T(dP/dT)H = -1
(dH/dP)T = -mJTCP
JT throttling is used to liquefy gases when mJT > 0 ( since dP < 0)

Inversion temperature: mJT > 0 below inv. T

 Inversion temperature: mJT > 0 below inv. T

atm cm6 mol-2 cm3 mol-1 Inversion T

Gas MW (kg/mol) a b diameter (å)
Ar 0.03995 1.34E+06 32.21 2.88 723
CH4 0.01604 2.26E+06 42.87 968
CO2 0.04401 3.61E+06 42.83 3.34 1500
H2 0.00202 2.45E+05 26.63 2.34 202
He 0.00400 3.41E+04 23.65 1.90 40
Kr 0.08380 2.29E+06 39.58 3.69 1090
N2 0.02801 1.35E+06 38.62 3.15 621
Ne 0.02018 2.09E+05 16.97 231
O2 0.03200 1.36E+06 31.67 2.98 764

JT throttling is used to liquefy gases when mJT > 0 ( since dP < 0)

U = Utr + Uvib + Urot + Uel + Uint + Unuc

Dependent on bonds in molecules

Bond Energy – Uel

difference between energy of AOs & MOs
Separated atoms
Energy

DUrx & DHrx

bond length

atom separation
 Standard Enthalpy of Reaction
DHo298 = Si ni Hom,298,i = Si ni Hom,298,i (products) - Si ni Hom,298,i (reactants)

CH4 + 2O2  CO2 + 2H2O

nCO2 = 1; nH2O = 2 nO2 = -2; nCH4 = -1

DHo298 = H˚CO2 + 2H˚H2O - H˚CH4 – 2H˚O2

Can’t know H˚i

U = Utr + Uvib + Urot + Uel + Uint + Unuc

Replace with DH˚f,298,i

 DHo298 = Si vi DHof,298,i
DHof,298,i = Standard Heat of Formation
The standard heat of formation of any element in its ‘natural’ state is
0.
This eliminates any concern over Unuc, and focuses on energy
differences due to bond formation.
e.g. C(gr) + O2(g) → CO2(g)

This can be experimentally determined using a bomb calorimeter, and is

the value listed in your thermodynamic tables = -393.5 kJ mol-1.
Bomb Calorimeter 1. Reaction heats water – DT measured
Requirements: 2. Cool to original T1
~ 100% Products
Power 3. T1 → T2; w = EIt = qrx = DUrx
exothermic
no side reactions Supply
w = EIt experiment
ignite DU = 0 step #1

R+K P+K
25 Co 25 + DToC

DUrx (298)
Uel
P+K
25oC
experiment
desired information step #2
Conversion from DUrx to DHrx
DHrx = DUrx + D(PV)
Only gases contribute significantly to D(PV)
Let D(PV) = DngRT …….

DHrx = DUrx + DngRT

Examples:
C(gr) + O2(g) → CO2(g) Dn = 0
CO(g) + ½ O2(g) → CO2(g) Dn = -½
 Cg + ½ O2(g) → COg
This can’t be done in a bomb calorimeter
Cg + O2(g) → CO2(g)

COg + ½ O2(g) → CO2

These can be done in a bomb calorimeter

DH˚rx = DH˚f,CO2 - DH˚f,CO
DH˚f,CO = DH˚f,CO2 - DH˚rx

Using similar procedures the values for DH˚f has been

determined for most common compounds and the results
can be found in standard thermodynamic tables.
 For a reaction at T  298K …….

dH = ∫ CP dT ~ CP DT

DHT – DH298 = ∫298T DCP,rx dT

DCPrx = Si ni DCPof,298,i

DHT = DH298 + DCP,rx (T – 298)

Note: you must keep units consistent: convert DCP,rx to kJ
 DH° DG° S° Cp°
Compound kJ mol-1 kJ mol-1 J mol-1 K-1 J mol-1 K-1
C(graphite) 0 0 5.74 8.527
C(diamond) 1.897 2.9 2.377 6.115
CH4 (g) -74.81 -50.72 186.264 35.309
CO (g) -110.525 -137.168 197.674 29.116
CO2 (g) -393.509 -394.359 213.74 37.11
C2H2 (g) 226.73 209.2 200.94 43.93
C2H4 (g) 52.26 68.15 219.56 43.56
C2H6 (g) -84.68 -32.82 229.6 52.63
C3H8 (g) -103.85 -23.37 270.02 73.51 Ethanol combustion
C6H6 (g) 82.93 129.7 269.31 81.67 at 298 K
glucose -1274.4 -910.1 212.1 218.8
ethanol(l) -276.98 160.67 -174.14 -180.92 at 500 K
Cl2 (g) 0 0 223.066 33.907
F2 (g) 0 0 202.78 31.3
H2 (g) 0 0 130.684 28.824
HD (g) 0.318 -1.464 143.801 29.196
D2 (g) 0 0 144.96 29.196
HBr (g) -36.4 -53.45 198.695 29.142
HCl (g) -92.307 -95.299 186.908 29.12
HF (g) -271.1 -273.2 173.799 29.133
HN3 (g) 294.1 328.1 238.97 43.68
H2O (l) -285.83 -237.129 69.91 75.21
H2O (g) -241.818 -228.572 188.825 33.577
H2O2 (l) -187.78 -120.35 109.6 89.1

DH = DH
H2S (g)
N2 (g) T
-20.63
0 298
+ DC -33.56
0 P,rx
(T – 298)
205.79
191.61
34.23
29.125
NH3 (g) -46.11 -16.45 192.45 35.06
Note: you must
NO (g) keep
90.25units consistent:
86.55 210.761 DCP,rx 29.844
convert to kJ
NO2 (g) 33.18 51.31 240.06 37.2
N2O4 (g) 9.16 97.89 304.29 77.28
O2 (g) 0 0 205.138 29.355
SO2 (g) -296.83 -300.194 248.22 39.87
PCl3 (g) -287 -267.8 311.78 71.84
PCl5 (g) -374.9 -305 364.58 112.8
If DHf,m,i is not in table …..
DHrx,298 can be estimated from tables of averaged bond energies.

DHº298 = Si -ni • bond energy (note sign is opposite)

AVG Bond Energy in kJ mol-1

C–C 344 C = C 615 H – H 436
C – Cgr 717 C = O 725 O – H 463 Ethanol combustion
C–H 415 C = N 615 N - H
C–O 350 N = N 418
C–N 292 O = O 498 O – O 143
C–F 441 N – N 159
C – Cl 328 C ≡ C 812 Cl – Cl 243
C – Br 276C ≡ N 890 F – F 158
C–S 259N ≡ N 946

Errors  as resonance energy  - particularly aromatic cpds