from “Atkins Physical Chemistry”, Atkins + de Paula, 10th Edition, 2014

HW Questions
1) Use the equipartition theorem to estimate the molar internal energy relative to U(0) of (i)
O3, (ii) C2H6, (iii) SO2 in the gas phase at 25 °C. (assume vibrational states inactive for
parts i. and iii., while 2 vibrational states are active for part ii.) 2A.1(b)

Answer:
(3 Marks possible – 1 for each correct answer, half credit for reasonable
attempt/steps)

1
Cv ,m  (3  vR*  2vV* ) R
2
with a mode active if T> ( where M isT , R, or V )
1
(i )O3 : Cv ,m  (3  3  0) R  3R [exp erimental  3.7 R]
2
E  3RT  3  8.314 J K 1 mol 1  298.15 K  7.436 kJ mol 1
1
(ii ) C2 H 6  Cv ,m  (3  3  2  2) R  5 R [exp erimental  6.3 R]
2
E  5RT  5  8.314 J K 1 mol 1  298.15 K  12.394 kJ mol 1
1
(iii ) SO2  Cv ,m  (3  3  0) R  3R [exp erimental  3.8R]
2
E  3RT  3  8.314 J K 1 mol 1  298.15 K  7.436 kJ mol 1

2) Which of (i) volume, (ii) heat, (iii) internal energy, (iv) density are state functions? 2A.2(b)

Answer: (i) volume, (iii) internal energy, and (iv) density are state functions.

(1 Mark possible, for all correct answers. 0.5 given if 2 correctly identified)
3) A sample consisting of 2.00 mol He is expanded isothermally at 0 °C from 5.0 dm3 to 20.0
dm3 (i) reversibly, (ii) against a constant external pressure equal to the final pressure of the
gas, and (iii) freely (against zero external pressure). For the three processes calculate q, w,
and ΔU. 2A.4(b)

Answer:
(3 Marks possible – 1 for each correct answer, half credit for reasonable
attempt/steps)

For all cases ΔU=0, since the internal energy of a perfect gas depends only on temperature.
From the definition of enthalpy, H = U + pV, so ΔH=ΔU+Δ(pV)=ΔU+Δ(nRT) (perfect
gas). ΔH=0 as well, at constant temperature for all processes in a perfect gas.
i.

U  H  0
V 
w  nRT ln  f  [ A2.9]
 Vi 
1 1 20.00 dm3
 (2.00 mol )  (8.314 J K mol )  273 K  ln 3
 6.29 103 J
5.00 dm
q   w  6.29 103 J
ii.
U  H  0
w   pex V [2 A.6]
where pex in this case can be computed from the perfect gas law
pV=nRT
(2.00 mol )  8.314 J K 1 mol 1  273 K
So P  3
 (10 dm m 1 )3  2.27 105 Pa
20.0 dm
(2.27 105 Pa)  (20.0  5.0) dm3
and w  3
 3.40  103 J
10.0 dm
q   w  3.40 103 J

iii.
U  H  0
w  0 [free expansion] q  U  w  0  0  0
Comment. An isothermal free expansion of a perfect gas is also adiabatic.
4) When 2.00 mol CO2 is heated at a constant pressure of l.25 atm, its temperature increases
from 250 K to 277 K. Given that the molar heat capacity of CO2 at constant pressure is
37.11 J K–1 mol–1, calculate q,  H, and  U. 2B.3(b)

Answer:
(3 Marks possible – 1 for each correct answer, half credit for reasonable
attempt/steps)

H  q p  C p T [2 B.2,2 B.7]  nC p ,m T
H  q p (2.0 mol ) (37.11 J K 1 ) (277  250) K 2.0 103 J mol 1
H  U   ( pV )  U  nRT so U  H  nRT
U  2.0 103 J mol 1 (2.0 mol )  (8.3145 JK 1 mol 1 )  (277  250) K
 1.6 103 J mol 1

5) For ethanol, vap H  = +43.5 kJ mol–1. Calculate q, w,  H, and  U when 1.75 mol
C2H5OH(l) is vaporized at 260 K and 765 Torr. 2C.1(b)

Answer:
(3 Marks possible – 0.5 for each correct answer, 1 for reasonable/correct attempt at
constructing equations)

At constant pressure
q  H  n vap H   (1.75 mol )  (43.5 kJ mol 1 )  76.1 kJ
and w   pV   pVvapor  nRT  (1.75 mol )  (8.3145 J K 1 mol 1 )  (260 K )
w  3.78 103 J  3.78 kJ
U  w  q  3.78  76.1  72.3 kJ
Comment. Because the vapor is treated as a perfect gas, the specific value of the external
pressure provided in the statement of the exercise does not affect the numerical value of
the answer.

6) The isothermal compressibility of lead at 293 K is 2.21 x 10-6 atm–1. Calculate the pressure
that must be applied in order to increase its density by 0.10 percent. 2D.4(b)

Answer:
(2 Marks possible – 1 for the correct answer; 1 for reasonable steps. Half credit for
reasonable attempt/steps without correct answer)
 1  V  V V
T      so p  
V  p T V p V T
A density increase of 0.10 per cent means V / V  0.0010 So the additional pressure that must
be applied is
0.0010
p   4.5 102 atm
2.21106 atm 1

7) Calculate the final temperature of a sample of carbon dioxide of mass 16.0 g that is
expanded reversibly and adiabatically from 500 cm3 at 298.15 K to 2.00 dm3. [Cp,m = 37.11
J K-1 mol-1 for CO2] (e.g. for a reversible adiabatic expansion) 2E.2(b)

Answer:
(2 Marks possible – 1 for the correct answer; 1 for reasonable steps. Half credit for
reasonable attempt/steps without correct answer)

For reversible adiabatic expansion:

1\ c
V 
T f  Ti  i  [2 E.2a ]
V 
 f 
Cv ,m C p ,m  R (37.11  8.3145) J K 1 mol 1
where C     3.463
R R 8.3145 J K 1 mol 1
therefore, the final temperature is
1\3.463
 500 103 dm3 
T f  (298.15)   3   200 K
 2.00 dm 
 8) It is sometimes appropriate to express the temperature dependence of the heat capacity by
the empirical expression C p,m     T   T 2 . Use this expression to estimate the
standard enthalpy of combustion of methane at 350 K. Use the standard enthalpy tables in
the back of your book in the “Resource Section” (you can also look this up on the internet)
and the following data for the empirical constants: 2C.7

 /( J K 1 mol 1 )  /( mJ K 1 mol 1 )  / (  J K 1 mol 1 )

CH4 (g) 14.16 75.5 -17.99
CO2 (g) 26.86 6.97 -0.82
O2 (g) 25.72 12.98 -3.868
H2O (l) 30.36 9.61 1.184

Note that for β: mJ = 10-3 J and for γ: μJ=10-6 J

Answer:
(3 Marks possible – 2 for correct answer, 1 for reasonable attempt/steps)
 r C p ,m   vC p ,m   vC p ,m
products reactants

CH 4 (g) + 2 O 2 (g)  CO 2 (g) + 2 H 2 O(l)

 r C p ,m  C p ,m (CO 2 )  2  C p ,m (H 2O)  C p ,m (CH 4 )  2  C p ,m (O 2 )
350 K
 r H m (350 K )   r H o m (Tstd )  
Tstd
 r C p ,m  dT

in the book the combustion standard is  r H o m (298 K )  890 kJ/mol

350 K
 r H m (350 K )   890 kJ mol 1     r C p ,m  dT
298 K
350 K 350 K 350 K 350 K
     
  r C p ,m  dT     vi i   dT     vi i   TdT     vi i   T 2 dT
298 K 298 K  i  298 K  i  298 K  i 
 1 26.86    2  30.36    2  25.72   114.16    T 298 
350

350
1 
1 6.97    2  9.61   2 12.98   1 75.5    T 2  
2  298
350
1 
1 0.82    2 1.184    2  3.868   1 17.99    T 3 
3  298
1 1
  21.98   350  298   75.27 10 3    350 2  2982    27.274 10 6    3503  2983 
2 3
  1142.96 J mol-1    1268.15 J mol-1    149.201 J mol-1   24.01 J mol -1
so  r H m (350 K )   890 kJ mol 1    24.01 J mol -1   890.02401 kJ mol-1  890 kJ mol-1

A lot of effort for little effect…but we did find ΔH for heating the reaction from 298 K to 350 K.
BONUS QUESTION(S), Optional +1 pt:

9) Rearrange the van der Waals equation of state, p  nRT / (V  nb)  n 2 a / V 2 to give an
expression for T as a function of p and V (with n constant). Calculate (T / p)v and
confirm that (T / p)v  1/ ((p / T )v . 2D.5

Go on to confirm Euler's chain relation.

Answer:
(a)
nRT n2a
p  2
V  nb V
 dp  nR
  
 dT V V  nb
 n2a  2
 1  pV pb na n ab
T  p,V n   p  2  V  nb        2
 V   nR  nR R VR V R
 dT  V b V  nb 1
     
 dp V nR R nR  dp 
 
 dT V

 dp  nRT 2n 2 a
   
 dV T (V  nb)
2
V3
V  nb n2a
T (p 2 )
nR V
 dT  1 n a 2n3ab
2

   ( p   )
 dV  p nR V2 V2

 dT   dp   dV   V  nb   nRTV 3  2n 2 a (V  nb) 2   nRV 3 

         
 dp v  dV T  dT  p  nR   (V  nb) V2 3
  pV  Vn a  2nab 
3 2

Assume n = 1

 dT   dp   dV  ( RTV 3  2aV 2  4abV  2ab 2 )(V  b)

      
 dp v  dV T  dT  p V RT  2aV  6abV  bV RT  6ab V  2ab
4 3 2 3 2 3

 1