CHM 2132 Midterm 1/10

Name:
Student Number:

CHM 2132
Midterm Test, October 24th 2008

This is a closed book exam with no notes allowed.

Calculators are permitted.
Write all the formulas that you use to solve the questions and show all
your work.
Remember to include units in all your calculations. Marks will be deducted if units are
not shown.

Data section and equation sheet available at the end of the

exam.
You can remove these pages and keep them.

Maximum score = 58/55 points

Please note that when re-

marking,
I will look at the full exam.
CHM 2132 Midterm 2/10

1. (11 points) 10 g of ethanol vapour (C2H5OH) is combusted under standard pressure at

298 K.
a) What is the total enthalpy of combustion for this reaction?

C2H5OH(g) + 3 O2(g) → 2 CO2(g) + 3 H2O(l)

°
Δr H =
m ∑ vΔ f H − ∑ vΔ f H m°
°
m
Products Reactants

(H O )+ 2Δ H (CO )− Δ H (C H OH )− 3Δ H (O )
° ° ° °
= 3Δ f H 2 (l) f
m m 2 (l) f m 2 5 (l) f m 2 (l)

( ) (
= 3 −285.83 kJ mol-1 + 2 −393.51 kJ mol-1 − −235.10 kJ mol-1 )( )
= −1409.41 kJ mol-1
Δ r H o = nΔ r H m°
m
= × Δ r H m°
M
=
10 g
46.07 g mol -1 (
−1409.41 kJ mol-1 )
= −310 kJ mol-1
kJ, not per mol

b) What would the total enthalpy be for combustion of liquid ethanol at the same
temperature?

( ) (
Δ r H m° liquid ethanol = Δ r H m° ethanol vapor + Δ vap H m° liquid ethanol) ( )
= −1409.41 kJ mol-1 + 43.5 kJ mol-1
= −1365.91 kJ mol-1
Δ r H o = nΔ r H m°
m
= × Δ r H m°
M kJ, not per mol
=
10 g
46.07 g mol-1
(
1365.91 kJ mol-1 )
= −296 kJ mol-1

c) What would be the total enthalpy for the combustion of the vapour at 350 K?

Δ r H (T2 ) = Δ r H (T1 ) + ∑ C prod

p ΔT − ∑ C p
react
ΔT

Δ r H (350 ) = −1409410 J / mol + 89.1J / Kmol (350 K − 298 K ) + 2(37.11J / Kmol )(350 − 298)
− 3( 29.36 J / Kmol )(350 − 298) − 64.44 J / Kmol (350 − 298)

Δ r H (350 ) = −1409410 + 4633.2 + 3547.44 − 4580.16 − 3350.88 = −1409160 J / Kmol

CHM 2132 Midterm 3/10

Δ r H (350 ) = −1409.16kJ / Kmol

for10 gΔ r H (350 ) = −305.87 kJ

2. (5 points) Estimate the standard enthalpy of formation of (CH3)3C-CClH-CH3 using

Benson thermochemical groups.

From left to right:

Δ f H = 3Δ f H (C (H )3 C ) + Δ f H (C (C )4 ) + Δ f H (C (Cl )(H )C 2 ) + Δ f H (C (H )3 C )
Δ f H = 3(− 42.17 ) + 8.16 + (− 60.2 ) + (− 42.17 )

Δ f H = −220.7 kJ / mol

3. (12 points)
a) Each one of the loops below represents a heat engine. Explain in ONE sentence which
engine is capable of producing more work and why.

The magnitude of work is given by the area inside the loop, therefore loop C is the one
capable of producing more work.

p
B

A
C

b) Mark the following statements as true or false.

NOTE: YOU WILL LOOSE MARKS FOR INCORRECT ANSWERS.
T/F
a) The internal energy of an ideal gas is independent of temperature. F
CHM 2132 Midterm 4/10

b) The total entropy of the universe is always increasing. T

c) A gas that expands spontaneously and irreversibly against an T
external pressure is performing work.
d) The change in entropy of a mixing process is always negative. F
e) The ΔG for a process in equilibrium is equal to zero. T
f) The ΔG0 for a process in equilibrium is equal to zero. F
g) The Helmhotz free energy change for a process provides the T
maximum amount of work that the process can do.
h) The Gibbs free energy change for a process provides an F
indication of spontaneity for constant volume processes.
i) ΔH for any phase transition is always positive. F

4. (7 points) Find the change in entropy for 2.50 mol of argon when it is cooled from 500
K to 300 K while at the same time expanding so that its pressure decreases from 4 bar to
1 bar.

ΔS T = ΔS1 (constant temperature) + ΔS 2 (constant pressure)

Since entropy is as state function, you can chose any path you like.

⎛V ⎞ ⎛T ⎞
ΔS T = nR ln⎜⎜ int ⎟⎟ + nC p ln⎜⎜ 2 ⎟⎟
⎝ V1 ⎠ ⎝ T1 ⎠

nRT1
Notice that the volume is changing, so the intermediate volume is Vint = if you
p2
follow this cycle (isothermal + isobaric).

nRT1
Also, V1 = , so
p1
CHM 2132 Midterm 5/10

⎛T ⎞ ⎛V ⎞ ⎛T ⎞ ⎛p ⎞
ΔS T = nC p ln⎜⎜ 2 ⎟⎟ + nR ln⎜⎜ int ⎟⎟ = nC p ln⎜⎜ 2 ⎟⎟ + nR ln⎜⎜ 1 ⎟⎟
⎝ T1 ⎠ ⎝ V1 ⎠ ⎝ T1 ⎠ ⎝ p2 ⎠

(
ΔS T = 2.5mol 20.77 JK −1mol −1 ln⎜ )
⎛ 300 K ⎞ −1 −1
(
⎛ 4bar ⎞
⎟ + 2.5mol 8.314 JK mol ln⎜ ⎟ )
⎝ 500 K ⎠ ⎝ 1bar ⎠

ΔS T = −26.5 JK −1 + 28.8 JK −1 = 2.3 JK −1

5 (6 points) 1.2 mol of an ideal gas is trapped in a piston at equilibrium with its
surroundings at 0.5 atm and 298.15 K. The gas then undergoes an isothermal reversible
expansion from a volume of 2.50 L to 10.0 L. The molar constant-volume heat capacity
of this gas is 27.5 J K-1 mol-1.

a) What is the final pressure of the gas? State your final answer in a sentence.

1.2mol * 8.314 JK −1mol −1 * 298.15 K

p2 = = 297458 Pa
10 L * 10 −3 m 3 L−1

(You could also do this as p1V1=p2V2)

b) What is the total work and the total heat of this process?

Vf ⎛ 10 ⎞
w = − nRT ln = −1.2mol * 8.314 J / Kmol * 298.15 * ln⎜ ⎟ = −4123 J = − q
Vi ⎝ 2.5 ⎠

c) Is it possible for this gas to do more work without giving the system any more energy?
Briefly explain your answer using p-V diagrams.

For expansion work, the maximum work that the gas can do is reversible. Therefore the
gas in this example cannot do more work.

6. (10 points) For the following reaction at 298 K, the partial pressures for the reactants
are 500 Pa for methane, 600 Pa for chlorine, 200 Pa for tetrachloromethane, and 850 Pa
for hydrogen. Will the reaction under these conditions tend to generate more products?
CHM 2132 Midterm 6/10

CH 4 (g ) + 2Cl 2 (g ) ↔ CCl 4 (g ) + 2H 2 (g )

solution

ΔrG0 = ∑νΔ f G 0 (prod ) − ∑νΔ f G 0 (react )

prod react
kJ kJ
Δ r G 0 = −58.2 + 50.72 = −7.48
mol mol

⎛
( )( ) ⎞
c d
pC pD
⎟
ΔG = ΔG + RT ln ⎜⎜
o po po
⎟
( )( )
a b
⎜ pA pB
⎟
⎝ po po ⎠
⎛ ⎛ 850 ⎞ 2 ⎛ 200 ⎞ ⎞
⎜⎜ ⎟ ⎜ ⎟⎟
⎛ ⎞ ⎜ ⎝ 101325 ⎠ ⎝ 101325 ⎠ ⎟
⎟(298K ) ln⎜
J J
Δ r G = −7480 + ⎜ 8.314 ⎟
mol ⎝ Kmol ⎠ 2
⎜ ⎛⎜ 600 ⎞⎟ ⎛⎜ 500 ⎞⎟ ⎟
⎜ 101325 ⎟
⎝⎝ ⎠ ⎝ 101325 ⎠ ⎠

J
Δ r G = −8024 Negative, therefore spontaneous as written.
mol
Reaction will generate more products.

Note that if you get to the same conclusion by comparing Q and K, that is ok also.

7. (4 points) In the first step of glucose metabolism the following two reactions are
coupled to give glucose-6-phosphate (G6P) and ADP under standard conditions at 25oC:

1) Glucose(aq) + phosphate(aq) → G6P(aq) + H2O(l) ΔGo = 14.3 kJ

2) ATP(aq) + H2O(l) → ADP(aq) + phosphate(aq) ΔGo = -31.0 kJ

a) What is the Gibbs free energy for the following reaction under standard conditions?

Glucose(aq) + ATP(aq) → G6P(aq) + ADP(aq)

Δ r G 0 = 14.3 − 31.0 = −16.7 kJ

b) Calculate the numerical value for the equilibrium constant for this reaction.

ΔrG o 16700
ln K = − (1) ln K = = 6.74 K=846
RT 8.314 * 298
CHM 2132 Midterm 7/10

8. BONUS (3 points) Calculate the isothermal compressibility coefficient at 5000 Pa, of a

gas whose compressibility is 0.5.

1 ⎛ ∂V ⎞ pV
κT = − ⎜ ⎟ Z= = 0.5
V ⎜⎝ ∂p ⎟⎠ T nRT

V = nRTZp −1 substitute and derive

κT = −
1
V
( )
1
− nRTZp − 2 = =
1
p 5000 Pa

Note: if you substituted the ideal gas law, it is wrong, even if in the end Z cancels out.
CHM 2132 Midterm 8/10

Data section:

STP = 0°C and 1 atm SATP = 298.15 K and 1 bar

1 atm = 1.01325 bar = 101325 Pa = 760 torr 1 L = 10-3 m3
R = 8.314 J K-1 mol-1

Δ f G 0 (CH 4 ) = −50.72kJ / mol Δ f G 0 (CCl 4 ) = −58.20kJ / mol

Δ f G 0 (Cl 2 ) = 0 Δ f G 0 (H 2 ) = 0
C p,m (H 2 O, g ) = 33.58JK −1mol −1 C p,m (H 2 O, l ) = 89.10JK −1mol −1
C p,m (Ar, g ) = 20.77JK −1mol −1 C p,m (CO 2 , g ) = 37.11JK −1mol −1
C p,m (CH 4 , g ) = 35.31JK −1mol −1 C p,m (O 2 , g ) = 29.36JK −1mol −1
C p ,m (CH 3CH 2 OH , g ) = 64.44 JK −1mol −1
C p ,m (CH 3CH 2 OH , l ) = 111.46 JK −1mol −1
Δ fusion H 0 (H 2 O, T = 273.15K ) = 6.01kJ / mol
Δ vaporization H 0 (H 2 O, T = 373.15K ) = 40.66kJ / mol
Δ combustion H 0 (CH 4 , g ) = −891kJ / mol
Δ vaporization H 0 (C 2 H 5 OH , T = 298.15 K ) = 43.50kJ / mol
( )
Δ f H mo H 2O(l) = −285.83 kJ mol-1 ( )
Δ f H mo H 2O(g) = −241.82 kJ mol-1
Δ H (CO ( g ) )= −393.51 kJ mol
f
o
m 2
-1
Δ f H mo (C H OH(g))= −235.10 kJ mol
2 5
-1

M (C H OH )= 46.07 g mol
2 5
-1

S0 (CO 2 , g ) = 213.8Jmol −1K −1 S0 (CH 4 , g ) = 186.3Jmol−1K −1

S0 (H 2O, l ) = 70.0Jmol−1K −1 S0 (O 2 , g ) = 205.2Jmol−1K −1

Δ f H mo (C(H)3(C)) = -42.17 kJ/mol

Δ f H mo (C(H)2(C)2) = -20.7 kJ/mol
Δ f H mo (C(H)(C)3) = -6.91 kJ/mol
Δ f H mo (C(C)4) = 8.16 kJ/mol
Δ f H mo (C(Cl)(H)(C)2) = -60.2 kJ/mol
CHM 2132 Midterm 9/10

Potentially useful formulas:

If a = f (x ) and b = f (x ) then d (ab ) = a ⋅ db + b ⋅ da

⎛ ∂a ⎞ ⎛ ∂a ⎞
If a = f (x , y ) then da = ⎜ ⎟ dx + ⎜⎜ ⎟⎟ dy
⎝ ∂x ⎠ y ⎝ ∂y ⎠ x

2
pV pVm nRT ⎛n⎞
pV = nRT Z= = `p= − a⎜ ⎟
nRT RT V − nb ⎝V ⎠
⎛ B (T ) C (T ) ⎞
pVm = RT ⎜1 + + 2 + ... ⎟
⎝ Vm Vm ⎠
dU = dw exp + dw other + dq ΔU = w + q ΔU = q v = C v ΔT
ΔU = q = IVt
Vf Vf
w = −∫ pdV w = −p ext ΔV w = − nRT ln
Vi Vi
⎛p ⎞
w = ΔU = C V ΔT w = −nR (TB − TA ) w = −nRT ln⎜⎜ A ⎟⎟
⎝ pB ⎠
H = U + pV dH = dU + d (pV ) dH = dU + d (nRT )
V
Δ H = q p = C p ΔT q = nRT ln f
Vi
⎛ ∂H ⎞ ⎛ ∂U ⎞ C p ,m
= a + bT +
c
(J K )
Cp = ⎜ ⎟ CV = ⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂T ⎠V
-1
mol -1
T2
γ −1 C p,m
TB ⎛ VA ⎞ C p − CV = nR γ=
=⎜ ⎟
TA ⎜⎝ VB ⎟⎠ C V ,m

⎛ ∂U ⎞ 1 ⎛ ∂V ⎞ ⎛ ∂T ⎞ 1 ⎛ ∂V ⎞
⎜ ⎟ = πT α= ⎜ ⎟ ⎜ ⎟ =μ κT = − ⎜ ⎟
⎝ ∂V ⎠T V ⎝ ∂T ⎠ p ⎝ ∂P ⎠ H V ⎜⎝ ∂p ⎟⎠ T
⎛ ∂U ⎞ ⎛ ∂U ⎞
dU = ⎜ ⎟ dV + ⎜ ⎟ dT dU = π T dV + C V dT
⎝ ∂V ⎠T ⎝ ∂T ⎠ V
⎛ ⎛ ∂x ⎞ ⎞ ⎛ ⎛ ∂x ⎞ ⎞
⎜ ∂⎜⎜ ⎟⎟ ⎟ ⎜ ∂⎜ ⎟ ⎟
⎛ ∂x ⎞ 1 ⎛ ∂x ⎞ ⎛ ∂y ⎞ ⎛ ∂z ⎞ ⎜ ⎝ ∂y ⎠ z ⎟ ⎜ ⎝ ∂z ⎠ y ⎟
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟ ⎜ ⎟ ⎜ ⎟ = −1 ⎜ ∂z ⎟ = ⎜ ∂y ⎟
⎝ ∂y ⎠ z ⎛⎜ ∂y ⎞⎟ ⎝ ∂y ⎠ z ⎝ ∂z ⎠ x ⎝ ∂x ⎠ y ⎜ ⎟ ⎜ ⎟
⎝ ∂x ⎠ z ⎜ ⎟ ⎜ ⎟
⎝ ⎠y ⎝ ⎠z
Δ r H (T2 ) = Δ r H (T1 ) + ∑ C prod
p ΔT − ∑ C p
react
ΔT
Δ r H0 = ∑νH0m (prod ) − ∑νH 0m (react )
prod react
Δ fus H = H (l ) − H ( s )
o o o
CHM 2132 Midterm 10/10

∫ w = (Thigh − Tlow )
∫ δ wrev = −∫ δ qrev Carnot − Efficiency =
q AB Thigh
dq rev dq
dS = dS ≥ dS Tot = dSsys + dSsurr
T T
N ⎛V ⎞ Δtrs H o
T2

Δ mix S = ∑ ni R ln ⎜ final
CV dT
⎜V ⎟⎟ Δtrs S o = ΔS = ∫
i =1 ⎝ i ,initial ⎠ Ttrs T1
T
T2
C dT N
⎛V ⎞
ΔS = ∫ p Δ mix S m = − R ∑ χ i ln χ i ΔS = nR ln ⎜ f ⎟
T1
T n =1 ⎝ Vi ⎠
⎛V ⎞
dA = dU − d (TS ) ΔA = −nRT ln ⎜ final ⎟
⎝ Vinitial ⎠
H = U + pV
dH = dU + d ( pV )
dG = dH − d (TS )
⎛p ⎞
ΔrG0 = ∑νΔ f G 0 (prod ) − ∑νΔ f G 0 (react ) G j ( p j ) = G j o + n j RT ln ⎜ oj ⎟
prod react ⎝p ⎠
⎛ pC
( )( ) ⎞
c d
⎛ ∂ ( ΔG / T ) ⎞
pD
⎜ po po ⎟ ΔH ΔrG o
ΔG = ΔG + RT ln ⎜
o
⎟ ⎜ ⎟ =− 2 ln K = −
( )( ) ∂T
a b
⎜ ppAo pB
⎟ ⎝ ⎠P T RT
⎝ po ⎠
⎛K ⎞ ΔH o ⎛ 1 1 ⎞
ln ⎜ 2 ⎟ = − ⎜ − ⎟
⎝ K1 ⎠ R ⎝ T2 T1 ⎠

dU = dw + dq = TdS − pdV
dH = dU + d(pV) = TdS − pdV + pdV + Vdp = TdS + Vdp
dA = dU − d(TS) = TdS − pdV − TdS − SdT = −pdV − SdT
dG = dH − d(TS) = TdS + Vdp − TdS − SdT = Vdp − SdT

⎛ ∂T ⎞ ⎛ ∂p ⎞ ⎛ ∂T ⎞ ⎛ ∂V ⎞
⎜ ⎟ = −⎜ ⎟ ⎜⎜ ⎟⎟ = ⎜ ⎟
⎝ ∂V ⎠S ⎝ ∂S ⎠ V ⎝ ∂p ⎠S ⎝ ∂S ⎠ p

⎛ ∂S ⎞ ⎛ ∂p ⎞ α ⎛ ∂S ⎞ ⎛ ∂V ⎞
⎜ ⎟ =⎜ ⎟ = − ⎜⎜ ⎟⎟ = ⎜ ⎟ = Vα
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V κ ⎝ ∂p ⎠ T ⎝ ∂T ⎠ p