CM1502 Tutorial 5

1) State the first law of thermodynamics in terms of

(a) the energy of the universe
(b) the creation or destruction of energy
(c) the energy change of system and surroundings.

Does the first law reveal the direction of spontaneous change? Explain.
(a) The total energy in the universe is constant.


1

(b) Energy cannot be created nor destroyed.


(c)


+DE
system
= -DE
surroundings
-DE
system
= +DE
surroundings
or
No, the first law is only concerned with the conservation of energy of a process and
says nothing about whether the process can be spontaneous or not.


2) Why is the work done when a system expands against a constant external pressure
assigned a negative sign?
3) Why is it more convenient to measure H than U?

It is assigned a negative sign as work is done by system for the expansion and
internal energy decreases.
U = q + w = -ve (if only consider w)


Since many reactions are performed in an open systems, the reaction proceeds at
constant pressure.
The determination of H only requires the measurement of heat at constant
pressure, whereas U requires the measurement of heat at constant volume or heat
and work.


2
CM 1502 3
DU = q
V
= C
V
x T
2

DH = q
P
= c
P
x mass x T
= (c
water
x mass
water
x T
water
)


H = U + PV = U + nRT
X
N2
=
) P P (P
P
O H N O
N
2 2 2
2

PV = nRT (ignoring the volume of the liquid)
K 293 x mol JK 8.314
) m 10 x 0.0015) - ((3.2 x Pa) 101325 x (0.02
RT
PV
1 - 1 -
3 -3

= 2.7 x 10
-3
moles
n =
0.6
0.02) 0.7 (0.5
0.7

4) A cylinder (3.2 L) at 20C contains a mixture of gases including O

2
at a partial
pressure of 0.5 atm and N
2
at a partial pressure of 0.7 atm. In the cylinder, there is
also 1.5 mL of H
2
O (l) at equilibrium with H
2
O (g). The vapour pressure of H
2
O (g) is
0.02 atm.

(a) What is the mole fraction of N
2
, X
N2
, in the vapour phase?
(b) Calculate the number of moles of H
2
O in the vapour phase (assuming ideal
conditions)?
4
Mr
m
1 -
gmol 18
g 1.5
n
total
= n
gas
+ n
liquid

n
total
= 2.7 x 10
-3
+ 8.3 x 10
-2
= 8.6 x 10
-2
moles
n
liquid
= =
= 8.3 x 10
-2
moles
(c) What is the total number of moles of water?
5
Density of water = 1 g mL
-1
6
5) A student would like to calculate the energy released from the combustion of a
banana. He uses a bomb calorimeter which has a heat capacity of 250 J K
-1

and 85% efficiency. The temperature increases 2.4 C. How many calories
are in the banana?
U = q
v
= C
v
T

= 250 x 2.4

= 600 J


600 J = 600 / 4.18 cal

= 143.5 cal




85% efficiency

143.5 / 85 % = 168.9 cal
6) When 1 mole of water at its boiling point evaporates at a constant pressure of
1 atm, it absorbs 9.7 kcal of heat. Owing to the volume change in going from
liquid to vapor, work is done by the system on the surrounding atmosphere.

(a) If the volume of a mole of liquid water is 0.019 liter at 373 K and water vapor
is an ideal gas, calculate the work done by the evaporation of 1 mole of liquid
water.
(b) What are the values of H and U for this process?
) V (V P w
1 2 ex

kJ 3.099
J 3099
) 10 0.019
101325
373 8.314
( 101325
3

(a)
kcal 9.7 q H
P

kJ 40.5
kJ 37.4
3.099 40.5

w q U
kJ 37.4
3.099) ( 40.5

OR



(b)
7
V P - H U
H = U + (PV)

H = U + (nRT)

2 x 11.3 kJmol
-1
= U + [(2 5) x (8.314 JK
-1
mol
-1
/ 1000) x 298 K]
U = 30.0 kJ / 2
U = 15.0 kJmol
-1

7) Calculate U
rxn
for the formation of N
2
O
5
(g) at 298 K, given that H
f
= 11.3 kJmol
-1

and it was formed by the following reaction:

4NO
2
(g) + O
2
(g) 2N
2
O
5
(g)
8
8) When 1 mole of methyl alcohol is converted at 298 K and constant volume
according to the reaction

CH
3
OH (l) + 3/2 O
2
(g) CO
2
(g) + 2 H
2
O (l)

173.65 kcal of heat is evolved. Give answers in kJ.

(a) What is H for this reaction?


kcal 173.65 q
v

U
kJ 725.86

(PV) U H
kJ 727.10
298) 8.314
2
1
( 725860


The reaction occurs at constant volume.




9

(nRT) U
] H 0
2
3
[ 4.18)] 94.05 ( 4.18) 68.32 2 [( H
OH(l) CH ,
0
f
3

10 . 727
727.10 28 . 964 H
0
OH(l) CH f,
3

kJmol 237.18
1



OH(g) CH OH(l) CH
3 3

kcal 8.43 H
vap
0

kJ 35.24
237.18 35.24 H
0
OH(g) CH f,
3

kJmol 201.94
1




(b) At 298

K, the H
o
f
of H
2
O (l) is 68.32 kcal, and for CO
2
(g), H
o
f
is
94.05 kcal. Calculate the standard enthalpy of formation of liquid methyl
alcohol.
(c) The enthalpy of vaporization of methyl alcohol is 8.43 kcalmol
-1
. Calculate
H
o
f
for CH
3
OH (g).


0
OH(l) CH f,
0
OH(g) CH f,
vap
0
3 3
H H H
10
] H 0
2
3
[ 4.18)] 94.05 ( 4.18) 68.32 2 [(
OH(l) CH ,
0
f
3

0
OH(l) CH f,
vap
0 0
OH(g) CH f,
3 3
H H H
CH
3
OH (l) + 3/2 O
2
(g) CO
2
(g) + 2 H
2
O (l)
H
2
O(l) H
2
O(s)
DH
T2
= DH
T1
+ DC
P
DT

C
p
= nC
p
(products) nC
p
(reactants)
C
p
= 8.8 calmol
-1
deg
-1
18.0 calmol
-1
deg
-1
C
p
= -9.2 calmol
-1
deg
-1

DH
T2
= DH
T1
+ DC
P
(T
2
T
1
)
DH
T2
= -1435 calmol
-1
+ -9.2 calmol
-1
deg
-1
(-10
o
C 0
o
C)
DH
T2
= -1343 calmol
-1
= -1343 x 4.18 Jmol
-1

= -5613.7 Jmol
-1

= -5.6 kJmol
-1
9) Calculate the enthalpy change when 1 mole of water freezes at constant
pressure and a temperature of -10
o
C. At 0
o
C, H is -1435 calmol
-1
and C
p
is
18.0 calmol
-1
deg
-1
and 8.8 calmol
-1
deg
-1
for water and ice, respectively. Give
answers in kJ.
11
Kirchhoffs Law is used to calculate H at
a different T.
12
Consider 2.00 moles of a monoatomic ideal gas that is
taken from state A (PA = 2.00 atm, VA = 10.0 L) to state B
(PB = 1.00 atm, VB = 30.0 L) by two different path ways:
Calculate q,w,E and H for both path ways.
10
State A
V
A
=10.0L
P
A
=2.00atm
V
C
=30.0L
P
C
=2.00atm
V
D
=10.0L
P
D
=1.00atm
State B
V
B
=30.0L
P
B
=1.00atm
1
2
3
4
13
W Q E H

Step 1 -2.00 x (30-10)
=-40 L atm
=-4050 J
1.01 x 10
4
J 6.08 x 10
3
J 1.01 x 10
4
J

Step 2

0 -4558.5 J -4558.5 J

-7597.5 J

Step 3

0 -1.52 x 10
3
J -1.52 x 10
3
J

-2.53 x 10
3
J
Step 4

-2.03 x 10
3
J 5.08 x 10
3
J 3.05 x 10
3
J

5.08 x 10
3
J

PV = nR T
T = 4050J/nR
qp = nCp T
=n(5/2) R(4050/nR)
qv = nCv T
=n(3/2) R(4050/nR)
PV = nR T
T = (1-2) x 30 x101.3/nR
qp = nCp T
=n(5/2) R(3039/nR)
qv = nCv T
=n(3/2) R(3039/nR)
14
w=-PV
q
p
=nC
p
T
E=nC
v
T
H=nC
p
T
Expansion
w= PV
q
v
=nC
v
T
E=nC
v
T
H=nC
p
T
compression
1L.atm = 101.31 J
15
When 1.00 L of 1.00 M Ba(NO
3
)
2
at 25.0C is mixed with 1.00 L
of 1.00 M Na
2
SO
4
at 25C in a calorimeter, the white solid BaSO
4

forms, and the temperature of the mixture increases to 28.1C.
assuming that the calorimeter absorbs only a negligible
quantity of heat, that the specific heat capacity of the solution
is 4.18 J C
-1
g
-1
, and that the density of the final solution is 1.0
g/mL, calculate the enthalpy change per mole of BaSO4
formed.
11
The balanced equation gives only one mole of BaSO4 .
Hence enthalpy of this reaction is the enthalpy per mole of BaSO4.
16
11.
Heat evolved by the reaction = heat absorbed by the solution
H = q
p
= specific heat capacity x mass of the solution
x increase in temperature.
= 4.18 X 2.0 x 10
3
x 3.1
= 2.6 x 10
4
J

Mass of the solution = 2.00 L x 1000 mL x 1gmL
-1
=2.0 x 10
3
g

Since the temperature increases the reaction is exothermic
and H should be negative = - 2.6 x 10
4
J
17
12 One kilogram of air initially at 300 K and 100 kPa
undergoes a quasi-equilibrium constant-pressure
process in a piston- cylinder assembly. If the final
temperature is 450 K, determine the work and
heat interactions and the change in enthalpy.
Assume air to be an ideal gas, R=0.287 kJ/kg/K
V
1
=
V
2
=
100kPa
1 kg x 0.287 kJ/kg /K 300K
100kPa
1 kg x 0.287 kJ/kg/K 450K
W =-p(V
2
-V
1
)
=-100 kPa (1.2915 0.861)m
3
=1.2915
=0.861
=-43.05 kJ
18
q=(U
2
U
1
)- w
=mCv(T
2
-T
1
)- w
=1 kg x 0.7165 kJ/kg K(450-300 )K (43.05)
=150.525kJ

H
2
-H
1
= mCp(T
2
-T
1
)
=(1kg)(1.0035 kJ/kg K) (450-300)K
=150.525 kJ
Note that in quasi equilibrium process, the heat interaction is equal to the change in
enthalpy of the system