PHYSICAL CHEMISTRY

A non ideal gas is heated slowly and expands

reversibly at a constant pressure of 275 torr
from a volume of 385 cm
3
to 875 com
3
. Find
W in joules.
PHYSICAL CHEMISTRY
A sample consisting of 1.0 mol of
CaCO
3
(s) was heated to 800
o
C, when it
decomposed. The heating was carried out
in a container fitted with piston that was
initially resting on the flat solid surface and
the whole container is under open
atmosphere.
Calculate the work done during complete decomposition reaction
at 1.0 atm.
PHYSICAL CHEMISTRY
One mol of the CO
2
gas product was
expanded reversibly and isothermally at
373 K from 5.25 to 6.29 cm
3
, and work
done of the gas sample was increased to
167 J. Using second coefficient, B, and
given work, calculate the second coefficient
of virial equation.
PHYSICAL CHEMISTRY
A mole of water vapor initially at 200
o
C and 1
bar undergoes a cyclic process for which
w=338 J. Calculate the q for this process.
PHYSICAL CHEMISTRY
The heat capacity of liquid chloroform,
CHCI
3
in the range of 240 to 330 K is given
by C
p,m
= 7.5 10
-2
T + 91.47 where Cp,m is
in J K
-1
mol
-1
, and T is in K. In a particular
experiment, 1.0 mol of CHCl
3
is heated from
273 to 300 K.
Calculate the change in molar entropy of the
liquid sample.
PHYSICAL CHEMISTRY
1.00 mol of perfectly behaved chloroform
vapour molecules at 65
o
C is expanded
isothermally from an initial pressure of 3.00
atm to a final pressure of 1.00 atm.
Determine the values of AH, AS, AS
tot
, AG
for reversible expansion.
PHYSICAL CHEMISTRY
The specific heat capacity of C
p
of water is
nearly constant at 1.00 (cal. /g
o
C) in the
temperature range 25
o
C to 75
o
C at 1 atm.
Calculate AS when 100g of water is
reversibly heated from 25
o
C to 50
o
C at 1
atm.
1
2
ln
T
T
C S
p
= A
}
= A
2
1
dT
T
Cp
S
}
= A
2
1
T
dq
S
rev
PHYSICAL CHEMISTRY
From standard enthalpies of formation,A
f
H
|
standard
entropies, S
m
|
and standard heat capacities, C
p,m

available from the appendix and by assuming that the
heat capacities are constant over the temperature range
involved, Calculate the standard enthalpies, and
entropies of the reaction: CO
2
(g) + H
2
(g) CO(g) +
H
2
O(g) at 298 and 398 K. Calculate A
r
G
|
(298K) by using
the Gibbs-Helmholtz relationship.
PHYSICAL CHEMISTRY
i , f i rxn
H H A v = A

Appendix
No component A
f
H
|
/ KJ .mol
-1
S
m
|
/ J K
-1
mol
-1
C
p,m
/ J .K
-1
mol
-1

1 CO
2
(gas) -393.51 213.79 37.11
2 CO (gas) -110.51 197.67 29.14
3 H (gas) 0 130.684 28.824
4 H
2
O(gas) -241.82 188.83 33.58
AH(H
2
O) + AH(CO) AH(H
2
)- AH(CO
2
)
i P i P
C C
,
= A

v
m i rxn
S S = A

v
rxn rxn rxn
S T H G A A = A
PHYSICAL CHEMISTRY
(a) Calculate q, w, AU and AH for the reversible
isothermal expansion at 300 K of 2.00mol of
perfect gas from 500 cm
3
to 1500cm
3
. what would
AU and w be if the expansion connects the same
initial and final stats as in (a) but is done by having
the perfect gas expand into vacuum?
PHYSICAL CHEMISTRY
Calculate the average value of AH
m
of vaporization of
water over the temperature range 25

C to 100

C. The
vapor pressure of water at 25

C is 23.76 torr.
|
|
.
|

\
|
~
1 2 1
2
1 1
ln
T T R P
P
m
H
ClausiusClapeyron equation
2
RT
H
dT
P ln d
m
A
~
PHYSICAL CHEMISTRY
Naphthalene, C
10
H
8
, melts at 80.2

C. If the vapour
pressure of the liquid is 1.95 kPa at 94.3

C and 5.47
kPa at 124.3

C, use the ClausiusClapeyron equation

to calculate enthalpy of vaporization, normal boiling
point and entropy of vaporization at the normal boiling
point.
2
ln
RT
H
dT
P d
m
A
~
R
H
T
d
P ln d
m
A
~
|
.
|

\
|

1
dT
T
T
d
|
.
|

\
|
=
|
.
|

\
|
2
1 1
Since
If AH is constant |
|
.
|

\
|
~
1 2 1
2
1 1
T T R
H
P
P
ln
m
A
PHYSICAL CHEMISTRY
Find AH
298
for the combustion of one mole of
glycine, (NH
2
CH
2
COOH), according to

NH
2
CH
2
COOH(s)+
9
4
O
2
(g)2CO
2
(g)+
5
2
H
2
O(l)+
1
2
N
2
(g)

AH
298
= E
i
v
i
A
f
H
298
,
i

PHYSICAL CHEMISTRY
Use the appendix, A
f
H
298
and S
m
data to
calculate A
f
G
298
for H
2
O(l). The formation
reaction is:

H
2
(g)+
1
2
O
2
(g)H
2
O(l), So


A
f
S
298
,
H
2
O(l)
= S
m,298
,
H
2
O(l)
- S
m,298
,
H
2
(g)
-
1
2
S
m,298
,
O
2
(g)


PHYSICAL CHEMISTRY
Calculate the number of moles of the
solute HCl in each of the following
aqueous solution

(a) 145mL of a solution with HCl molarity 0.800mol/dm
3
(b) 145g of a 10 weight percentage HCl Solution
(c) 145g of solution whose HCl molality is 4.85 mol/kg
PHYSICAL CHEMISTRY
At 20

C, P
o
benzene
=74.7 torr and P
o
toluene
=22.3 torr. A
certain solution of benzene and toluene at 20
o
C has
a vapour pressure 46.0 torr. Find the benzene mole
fraction in this solution and in the vapour above this
solution.
Let, benzene = b and toluene =t
Total pressure P
Tot
=P
b
+ P
t

From Raoults law,
P
b
= x
b
P
o
b
P
t
= x
t
P
o
t
P
Tot
=P
b
+ P
t
=x
b
P
o
b
+ x
t
P
o
t

=x
b
P
o
b
+ (1-x
b
)P
o
t
,where(x
A
+ x
B
=1)
PHYSICAL CHEMISTRY
P
Tot
= x
b
P
o
b
+ (1-x
b
)P
o
t
,where(x
A
+ x
B
=1)
46.0torr= x
b
(74.7torr) + (1-x
b
)(22.3torr)

x
b
=0.452 (mole fraction of benzene in the sol.)
partial vapour pressure of benzene in solution, P
b

P
b
= x
b
P
o
b

=(0.452)(74.7torr)
=33.8torr
Daltons Law
P
b
=y
b
P
Tot
Y
b
= P
b
/P
Tot
=
33.8torr/46.0torr
=0.735
Mole fraction of benzene
in vapour phase is
y
b
= mole fraction of component B in the vapour
P
b
=partial vapour pressure of component B
P
Tot
= P
b
+ P
a
= Total pressure of the system
PHYSICAL CHEMISTRY
Vapour pressure of pure liquid A and B at 50

C
are 37.38 kPa and 42.17 kPa respectively.
Solution with mole fraction of X
B
= 0.0579 gives
partial pressure of A and B of 35.48 kPa and 3.73
kPa respectively. Calculate the activity coefficient
of A and B based on both Raoult's and Henry's
Laws.
the solubility of a gas in a liquid is directly proportional to the partial pressure of the gas
above the liquid
PHYSICAL CHEMISTRY
The data for the transformation of ammonium cyanate (NH
4
CNO)
to form urea (NH
2
CONH
2
) with the chemical reaction of NH
4
CNO
NH
2
CONH
2
is given in TABLE Q3. Initially 22.9 g of
ammonium cyanate was dissolved in enough water to prepare
1.00 dm
3
of solution.

Reaction time, (t/min) 0 20.0 50.0 65.0 150.0
Mass of NHCNO, (m/g) 22.9 15.9 10.8 9.1 5.2
TABLE Q3: Transformation of ammonium cyanate into urea with the time.
Given that M
urea
= M
ammonium cyanate
= 60 g/mole.
Propose the order of reaction. Justify your answer.
Calculate the rate constant.
Calculate the mass of ammonium cyanate left after 400 min.
PHYSICAL CHEMISTRY
Q:Write the rate expressions for the following
reactions in terms of the disappearance of the
reactants and the appearance of the products.

4NH
3
(g) + 5O
2
(g) 4NO (g) + 6H
2
O (g)





PHYSICAL CHEMISTRY
2DI D
2
+ I
2
has k = 1.2 10
-3
dm
3
/mol
3
at 660 K and E
a
= 177 kJ/mol.
Calculate k at 720 K.
(

= =
=
2 1
1
2
1
2
1 1
/
/
/
T T R
E
RT E
RT E
T
T
RT E
a
a
a
a
e
Ae
Ae
k
k
Ae k

|
|
.
|

\
|
=
(

K K molK J
mol J
e
s mol
dm
k
720
1
660
1
/ 314 . 8
/ 10 77 . 1
3
3
720
5
.
10 2 . 1
s mol
dm
.
10 8 . 1
3
2
=
PHYSICAL CHEMISTRY
The values of rate constant, k for the given
below reaction are 1.2 10
-3
and 3 10
-5

dm
3
.mol
-1
.s
-1
at 700 K and 629 K, respectively.
Calculate the activation energy, E
a
of this
reaction.
2HI(s) H
2
(g)+ I
2
(g)