PHYSICAL CHEMISTRY

Final Output Probsets

Submitted by:

Agacer, Neel Godwin D. - 201913581

Matibag, Kienth G. - 201913948
Tongo, Jhon Nicko Y. - 201912842
Tripon, Casey Lance D. - 201912267

Submitted to:
Engr. Clyde Lopez
I. Basic Concepts (Tongo)
1. A sample of an unknown material weighs 54.8 and has a volume of 7.84 ml. It has
______.

Lead Sulfide (ρ = 7.56 g/ml) Cinnabar (ρ = 8.10 g/ml)

Sphalerite (ρ = 4.0 g/ml) Cassiterite (ρ = 6.99 g/ml

Platinum (ρ = 21.4 g/ml)

Given: Mass of mineral = 54.8 g Required: Density (ρ)

Volume of mineral = 7.84 ml

mass of mineral
Solution: ρ =
Volume occupied by mineral

54.8 g
ρ=
7.84 ml

ρ = 6.99 g/ml

Cassiterite (ρ = 6.99 g/ml)

2. A gasoline line is connected to a pressure gage through a double-U manometer. If the
reading of the pressure gage is 370 kPa, determine the gage pressure of the gasoline line.
[Gasoline SG = 0.70 (45cm × 50cm) Pipe Air (22cm × 10cm) Water ‘Mercury SG =
13.6]

Given: ρ gage = 370 kPa ρoil = 790 kg/m3 ρ gasoline = 700 kg/m3

ρwater = 1000 kg/m3 ρ Hg = 13600 kg/m3

Required: Gage Pressure ( Pg )

Solution:

Pgage −ρwater × g × 0.45+ ρoil × g × 0.5− ρHg × g ×0.1−ρgasoline × g ×0.22=P g❑

Pg =37000−(4414.5)+( 3874.95)−(13341.6)−(1510.74)

Pg = 354.608 kPa
3. A gasoline line is connected to a pressure gage through a double-U manometer. If the
reading of the pressure gage is 370 kPa, determine the gage pressure of the gasoline line.
Gasoline SG = 0.70 (45cm × 50cm) Pipe Air (22cm × 10cm) Water ‘Mercury SG =
13.6

Given: Reading of gage pressure = 28.2

Barometric Pressure = 751 mm Hg

Required: Absolute pressure in kPa, psi, and psf

Solution: P|¿|= P gage +P atm ¿

¿ 28.2 mm Hg+751 mm Hg

¿ 779.2 mm Hg

¿ 779.2 mm Hg × ( 0.1333
1 mm Hg )
kPa
=¿
103.8673 kPa

15.0385 psi
¿ 779.2 mm Hg × (
0.0193 psi
1 mm Hg
=¿ )
2166.176 psf
¿ 779.2 mm Hg × (
2.78 psf
1 mm Hg
=¿)
4. A vacuum gauge mounted on a condenser reads 660 mm Hg. What is the absolute
pressure in the condenser in kPa when the atmospheric pressure is 101.325 kPa?

Given: Patm =101.325 kPa Pgage =660 mm Hg

Required: Absolute pressure

Solution: 1 mm Hg=0.1333 kPa

G=660mm Hg × ( 0.1333
1 mm Hg )
kPa

G=88 kPa

P|¿|= P atm −Pgage ¿

P|¿|=101.325 kPa−88 kPa ¿

P|¿|=¿ ¿ 13.325 kPa

5. A bourdon pressure gauge is connected to a large tank and reads 440 kPa when the
barometer reads 750 mm Hg. What will the gauge be if the atmospheric pressure increases
to 765 mm Hg?

Given: Pgage =440 kPa Patm =765 mm Hg

Reading Barometer = 750 mm Hg

Required: Absolute and gage pressure

Solution: Case-I

P
|¿|=(440× 103 )+750 ×
(101325
760 )
¿

P|¿|=¿ ¿ 539991.78 Pa

Case-II

P|¿|= P gage +P atm ¿

Pgage =P|¿|− P atm ¿

¿ 539991.78−765 × ( 101325
760 )
≃ 438000.16 Pa

≃ 438 kPa
6. A vacuum gage connected to a chamber reads 5.8 psi at a location where the atmospheric
pressure is 14.5 psi. Determine the absolute pressure in the chamber.

Given: Patm =14.5 psi Pgage =5.8 psi

Required: Absolute Pressure

Solution: P|¿|= P atm −Pgage ¿

P|¿|=14.5 psi−5.8 psi¿

P|¿|=¿ ¿
8.7 psi
II. Gases (Tongo)

1. Pressurized air cans are used to blow dust out of electronic equipment. At 300.0 K the air
can’s pressure is 2.00 atm. If the can was to reach 6.00 atm’s of pressure it will explode.
What temperature must the air reach in order for the can to explode?
Given:
P1=2.00 atm P2=6.00 atm
T 1=300.0 K T 2=?
Required: Final Temperature
Solution:
P 1 V P2 V P 1 P2
= → =
T1 T2 T1 T 2

300,0 K ) ( T
( 2.00 )
atm 6.00 atm
=
2

T 2= ( ( 6.00900atm ) ( 300.0 K )
2.00 atm
K
)
T 2=¿
2. A sample of neon has a volume of 0.730 dm 3 at a temperature of 21.0°C and pressure of
102.5 kPa. If the density of neon is 0.900 g/dm 3 at 0°C and 101.3 kPa, what is the mass of
the sample?
Given:
P1=102.5 kPa P2=101.3 kPa
V 1=0.730 dm3 V 2=?
T 1=21.0 °C T 2=0 ° C
Required: mass of the sample
Solution:
Cross-multiplied of the combined gas law:
P1V 1 P2V 2
=
T1 T2
P1 V 1 T 2=P2 V 2 T 1
( 102.5 kPa ) ( 0.730 dm 3 ) ( 273 K ) =( 101.3 kPa ) ( V 2) ( 294 K )
3
V 2=0.685887 dm
Determine mass:
0.685887 dm ( 0.900 g /dm ) =¿
3 3
0.617 g
3. A gas sample has a mass of 9.98 g. Its volume is 21.6 L at a temperature of 75.46°C and a
pressure of 641 torr. Find its molar mass
Given:
L atm
P = 641 torr = 0.843 atm R = 0.08206
mol K
V = 21.6 L T = 75.46°C = 348.61 K
Required: molar mass
Solution:
PV
PV =nRT → n=
RT
PV ( 0.843 atm ) ( 21.6 L )
n= =
RT
( 0.08206 )
Latm
mol K
( 348.61 K )

n=0.636 mol
m 9.98 g
M= = =¿ 15.7 g/mol
n 0.636 mol
4. A mixture of gases exists at a total pressure of 775 kPa. If 25% of the pressure is due to
oxygen, and 30% of the pressure is due to nitrogen, what is the partial pressure of
hydrogen?
Given:
The total pressure of the gas mixture = 775 kPa
The partial pressure of the oxygen gas = 25%
The partial pressure of the nitrogen gas = 30%
Required: partial pressure of hydrogen
Solution:
Σ P=PO + P N + PH
2 2 2

% partial pressure of H 2 = total pressure - (% partial pressure of O2 + % partial pressure

of N 2)
% partial pressure of H 2=100−( 25+30 ) =45 %
% ∂ pressure of H 2
The ∂ pressure of H 2= × total pressure of mixture
100
The ∂ pressure of H 2=( )45
100
× 775
349
The kPa of H 2=¿
∂ pressure
5. What is the molar volume, liters/mole of ethylene at 25°C and 12 bar according to (a)
Berthelot equation and (b) Dieterici Equation?
Given:
T = 298 K P = 11.8431 atm (12 bar)
Tc = 282.3 K Pc = 49.346 atm (50.4 bar)
Required: Berthelot equation and Dieterici Equation
Solution:
Berthelot Equation Dieterici Equation

[ ( ) ]
2
6TC

PV =RT
1+9 PT C 1−

128 PC T
T
2
[ ( )]
P(V −b) exp
a
VRT
=RT

Berthelot Equation

[ ( ) ]
2❑
6 ⋅ (282.3 )
1+ 9 (11.843 )( 282.3 ) ⋅ 1− 2
( 298 )
11.843 V =0.082 ⋅298
128 ⋅ 49.346 ⋅298
22.7233
11.843 V =22.7233 →V =
11.843
1.9187 liters/mol V =¿
6. Express Redlich-Kwong equation of the state in the virial form equation of state.
RT a
Solution: P= −
V −b √ T V ( b +V )

[( ]
RT 1 a
P= −
V b ( ) b +1
)
3
1−
V VR T 2
V ( )
[( ) ( 1+ )
]
−1 −1
b a b
PV =RT 1− −
V ()
3
2
V
VR T

PV =RT 1−
[( ) ( ( ) ) ( ( ) )(
(
VR T 2
a
3
)
+ 1+
VR T
a
3
2
b
V
1−
a

VR T
3
2
b 2
V )
+...
]
[ ( ( )) ( ( )) ( ( )) ]
2
a 1 2 ab 1 −a b 1
PV =RT 1+ b− + b+ + +... (1 )
3
2
V 3
2
V 2 3
2
V 3

RT RT RT

PV =RT 1+ B
1
V [ () () ]
+C
1 2
V
+ ... (2 )

Comparing Eq. 1 and 2

(
B= b−
RT
a
()
3
2 ) C=

The virial form equation of state under Redlich-Kwong Equation is:

[ ( 1
V
2
+ b+
ab

RT
( 2)
3
)]
PV =RT 1+ b−
[( ) ( RT
a
()
3
2
1
V
+ b2 +
ab

RT
( 3
2 ) )
V
1
2
+ ....
]
III. Thermodynamics “1st Law of Thermodynamics” (Tongo)

1. A sample of an ideal gas at 15.0 atm and 10.0 L is allowed to expand against a constant
external pressure of 2.00 atm at a constant pressure. Calculate the work in units of kJ for
the gas expansion.

Given:
P1=15.0 atm P2=2.00 atm
V 1=10.0 L
Required: work in units of kJ for the gas expansion
Solution:
W exp =−Pext ⋅ ΔV =−Pext ⋅ ( V final−V Initial )
P1 V 1=P2 V 2

V 2=
P2
= [
P1 V 1 ( 15.0 atm ) ( 10.0 L )
2.00 atm ]
=75 L

( )
J
8.314
mol ⋅ K
W =−2.00 atm ⋅ ( 75 L ) ⋅
-15.2 kJ 0.0821
L ⋅atm
mol ⋅ K
W =¿
2. 500 J of heat energy was absorbed from the surroundings and the gas expanded from 30L
to 70L against a constant pressure of 2.8 atm. Calculate the internal energy change in
joules.
Given:
q = 500 J V i=30 L
P=2.8 atm V f =70 L
Required: internal energy change in joules
Solution:
W =−PΔV
W =−P [ V f −V i ]
W =−2.8 atm [ 70 L−30 L ]

W =−112 L ⋅atm ⋅ (
101.3 J
L ⋅ atm )
W =−11345.6 J
q=500 J
Δ U =q+ w
¿ 500 J +(−11345.6 J )
Δ U =¿ -10845.6 J
3. The temperature of a sample of ideal gas increased from 300K to 500K. Calculate the
change of the internal energy if there were (a) 5 moles of a monoatomic gas and (b) 8
moles of diatomic gas in the sample.
Given:
3
T f =500 K n of monoatomic gas=5 moles Cv= R
2
T i=300 K n of diatomic gas=8 moles
Required: internal energy between monoatomic and diatomic gas
Solution:
a) Monoatomic Gas b) Diatomic Gas
3 3
Δ U =nCvΔT → ΔU = nRΔT Δ U =nCvΔT → ΔU = nRΔT
2 2
3 3
Δ U = ( 5 ) ( 8.3145 ) (200 ) Δ U = ( 8 ) ( 8.3145 ) ( 200 )
2 2
Δ U =¿ 12472 J Δ U =¿ 33258 J
4. When a sample of 1.0 mol of a monoatomic perfect gas with C v ,m =12.47 J /mol K and
initially at 25°C, doubles it volume adiabatically its temperature decreases to -60°C. State
whether the process is reversible or not. Why?
Given:
Amount of sample in moles = 1 mol T i=25 ° C=298.15 K
C v ,m for monoatomic gas = 12.47 J/mol K T f =−60 °C=213.15 K
Required: Reversible adiabatic process
Solution:
γ−1 γ −1
T 1 ⋅ ( V 1 ) =T 2 ⋅ ( V 2 )
C
γ= P → C P−C v =R
Cv
CP R
−1=
Cv Cv
R
γ−1=
Cv
8.314 J K −1 mo l−1
γ−1=
12.47 J K −1 mo l−1
γ−1=0.66

( )
0.66
298.15 2 v 0.66
= →1.3990=( 2 )
213.15 v
1.4 = 1.5
5. Calculate the work done during the isothermal reversible expansion of a gas that satisfies
the virial equation of state written with the first three terms. Evaluate (a) the work for 1.0
mol Ar at 273 K and (b) the same amount of a perfect gas.
Given:
3
Mole of Argon = 1.0 mol V i=500 c m
3
T =273 K V f =1000 c m
Required: work and same amount of a perfect gas.

Solution: w=−RT × ln + [
V f 21.7 21.7
Vi V f
−
Vi ]
{ }
Vf
RT B (T )
p= 1+ → ( Eq .1 ) w=−∫ ❑ pdV → ( Eq .2 )
Vm Vm Vi

Substitute at Eq. 2

[ { }] [ ]
Vf Vf
RT B (T ) 1 21.7 c m3 mol −1
w=−∫ ❑ 1+ dv →−RT ∫ ❑ −
V Vmi
Vm V Vm V 2m i

w=−8.314 J K −1 mo l−1 (273 K)× ln

-1.523 kJ
[ 1000 c m3
3
+
21.7
3
−
21.7
500 c m 1000 c m 500 c m3 ]
w=−1523.66 J ≈
6. A 14.0 g of nitrogen gas at 20.0 oC and a pressure of 2.0 atm is isothermally compressed to
a pressure of 15.0 atm. Calculate (a) the change in thermal energy, and (b) show the
process on a PV diagram.
Given:
m of Nitrogen = 14.0 g T = 293.15 K
No. of moles of Nitrogen = 0.5 mol V of Nitrogen = 6.01 L
Pi = 2.0 atm Pf = 15.0 atm
Required: change in thermal energy, and PV diagram
Solution:
nRT 0.5 ⋅0.0821 ⋅ 293.15
V= = Δ U =Q+W
P 2
V =6.01 L Q+W =0 →Q=−W =¿ -4.91 kJ
P1 V 1 2⋅ ( 6.01 )
V 2= =
P2 15
V 2=0.80 L

W =RTln ( )
P2
P1

¿ 8.314 × 293.15 ln ( 152 )

W =4908.307 J ≈ 4.91 kJ
● 2nd Law of Thermodynamics (Agacer)
1. Calculate ΔS (for the system) when the state of 2.00 mol diatomic perfect gas molecules,
7
for which Cp = R , is changed from 25℃ and 1.00 atm to 125℃ and 5.00 atm. How do
2
you rationalize the sign of ΔS?
Given:
7
n = 2.00 mol Cp = R T1 = 25℃ ~ 298.15 K
2

P1 = 1.50 atm T2 = 135℃ ~ 408.15 K P2 = 7.00 atm

Solution:
T2
❑
dQ C p dT T2
ΔS1 = ∫ ❑ ∫❑ = Cp ln[ ]
❑ T T1
T T1
7 −1 −1 408.15 K
→ ΔS1 = (2.00 mol)[( )(8.314 J K mol )](ln[ ¿) = 18. 27638575 JK-1
2 298.15 K

❑
dQ Q
❑
V2 P1
ΔS2 = ∫ ❑ = ; where Q = (-w) = ∫ ❑PdV = -nRln[ ] = nRln[ ]
❑ T T ❑ V1 P2
P1
thus, ΔS2 = nRln[ ]
P2
1.50 atm
→ ΔS2 = (2.00 mol)(8.314 JK-1mol-1)(ln[ ]) = -25.61452014 JK-1
7.00 atm

ΔStot = ΔS1 + ΔS2

→ ΔST = [18.27638575 + (-25.61452014)] JK-1 = -7.33813439 JK-1
2. Calculate the molar entropy of a constant-volume sample of argon at 250 K given that it is
154.84 J K-1 mol-1 at 298 K.
Given:
T2 = 500 K T1 = 298 K S(298 K) = 154. 84 J K-1 mol-1
Solution:
Cp = Cv + R → Cv = Cp - R
→ Cv = (20. 786 - 8. 314) JK-1mol-1 = 12. 472 JK-1mol-1

T2
dT T2
S(T2) = S(T1) + Cv + ∫ ❑ = S(T1) + Cvln[ ]
T1
T T1
250 K
→ S(250 K) = 154. 84 JK-1mol-1 + 12. 472 JK-1mol-1 (ln[ ]) = 152. 6495106 JK-1mol-1
298 K
3. Calculate the change in entropy when 50 kJ of energy is transferred reversibly and
isothermally as heat to a large block of copper at (a) 0 °C, and (b) 70 °C.
Given:
q = 50 kJ ~ 50000 J Ta = 0°C ~ 273. 15 K Tb = 70°C ~ 343. 15 K
Solution:
❑ ❑
dQ 1 Q
ΔS = ∫ ❑ = ∫ ❑dQ =
❑ T T ❑ T
50000 J
→ ΔSa = = 183. 0496064 JK-1
273.15 K

50000 J
→ ΔSb = = 145. 7088737 JK-1
343.15 K
4. Consider a system consisting of 1.50 moles of CO 2(g), initially at 15°C and 9.0 atm and
confined to a cylinder of cross-section 100.0 cm 2. The sample is allowed to expand
adiabatically against an external pressure of 1.5 atm until the piston has moved outwards
through 15 cm. Assume that carbon dioxide may be considered an ideal gas with a C v =
28.8 J K-1 mol-1, and calculate (a) q, (b) w, (c) ΔU, (d) ΔT, (e) ΔS.
Given:
T1 = 15°C ~
n = 1.50 mol CO2 Pi = 9 Atm A = 100 cm2
288.15 K

Pex = 1.5 atm Cv = 28.8 JK-1mol-1 L = 15 cm

Solution:
→ Q = 0 J (since the process is adiabatic)

101325 Pa
→ w = -PexΔV = - [1.5 atm× ] ¿ = -227.98125 J
1 atm

→ ΔU = q + w = -227. 98125 J

ΔU −227.98125 J
→ ΔU = w = nCvΔT, thus ΔT = = = -5.27734375 K
n C v (1.5 mol)(28.8 J K−1 mol−1 )

ΔS = nCvln ( )
T2
T1
+ Rln ( )
V2
V1
 (1.5 mol)(0.08206 L atm mol−1 K −1 )(288.15 K)
→ V2 = = 3.9409315 L ~ 0.0039409315 m3
9 atm
→ V2 = 0.0039409315 m3 + 0.0015 m3 = 5.4409315×10-3 m3
→ T2 = [288.15 + (-5.27734375)] K = 282.8726563 K
→ ΔS = (1.5 mol)[(-0.5323495464) + 2.681540702] JK-1mol-1 = 3.223786733 JK-1

5. The heat capacity of chloroform (trichloromethane, CHCl3) in the range of 240 K to 330 K
is given by Cp /(JK-1mol-1) = 91.47 + 7.5×10-2 (T/K). In a particular experiment, 1.00 mol
CHCl3 is heated from 273 K to 300 K . Calculate the change in molar entropy of the
sample.
Given:
Cp = 91.47 + 7.5×10-2
n = 1.00 mol T1 = 273 K T2 = 300 K (T/K)
Solution:
S2 T2 T2
dH dH C dT
dS = → ∫ ❑dS = ∫ ❑ → (S2 - S1) = ∫ ❑ p
T S 1 T
T 1 T
T 1

T2
C p dT
thus; ΔS = ∫ ❑
T1
T
300 K 300 K
91.47+7.5 ×1 0−2 T dT 91.47 7.5× 10−2 dT 300 K
→ ΔS = ∫ ❑
T
= ∫ ❑
T
+
T
= 91.47[ln
273 K
] +(7.5×10 -

273 K 273 K
2
)[(300 - 273)] K = 10.651 JK-1mol-1
6. Calculate the standard reaction of entropy at 298 K of
(a) Zn(s) + Cu+2(aq) = Zn+2(aq) + Cu(s)
(b) C12H22O11(s) + 12 O2(g) = 12 CO2(g) + 11 H2O(l)
Solution:

∑Sr = ∑S(products) - ∑S(reactants)

→ (a) [(-112.1)+(33.150)] - [(-99.6)+(41.63)] JK-1mol-1 = -20.98 JK-1mol-1

→ (b) [11(69.91) + 12(213.74)] - [12(205.138) + (360.2)] JK-1mol-1 = 512.034 JK-1mol-1

7. A sample of copper of mass 2.75 kg is cooled at constant pressure from 330 K to 275 K.
Calculate the energy that must be removed as heat and the change in the entropy of the
sample.
Given:
 m = 2.75 kg Cu T1 = 330 K T2 = 275 K
Solution:

Q = nCpΔT

1 mol Cu
→ Q = [2.75 kg × ](24.44 JK-1mol-1)(275 - 330) K = -58171.24603 J
0.063546 kg

( )
T
❑
dQ C dT
2
T2
ΔS = ∫ ❑ = ∫❑ p = Cpln
❑ T T
T1
T1

→ ΔS = [2.75 kg ×
1 mol Cu
0.063546 kg [ ( )]
](24.44 JK-1mol-1) ln
275 K
330 K
= -192. 8340388 JK-1

8. A sample of 3.00 mol of diatomic perfect gas molecules at 200 K is compressed reversibly
and adiabatically until its temperature reaches 250 K. Given that the C v = 27.5 J K-1 mol-1,
calculate q, w, ΔU, ΔH, and ΔS.
Given:
 n = 3 mol Cv = 27. 5 J K-1 mol-1 T1 = 200 K T2 = 250 K
Solution:
→ Q = 0 J (since the process is adiabatic)

→ ΔU = nCvΔT = (3 mol)(27.5 JK-1mol-1)(250 - 200) K = 4125 J ~ 4.125 kJ

→ w = ΔU = 4125 J (from 1st Law)

ΔH = nCpΔT
→ Cp = Cv + R = (27.5 + 8.314) JK-1mol-1 = 35.814 JK-1mol-1

→ ΔH = (3 mol)(35.814 JK-1mol-1)(250 - 200) K = 5372.1 J ~ 5.3721 kJ

ΔS = 0 JK-1

9. Calculate the Carnot efficiency of a primitive steam engine operating on steam at 180 °C
and discharging at 100 °C. Repeat the calculation for a modern steam turbine that operates
with a steam at 360 °C and discharges at 100 °C.
Given:
Steam Engine Modern Steam Engine

Tc = 180 °C ~ 453. 15 K Tc = 360 °C ~ 633. 15 K

 Th = 100 °C ~ 373. 15 K Th = 100 °C ~ 373. 15 K
Solution:
Tc
Ɛ=1-
Th
373.15 K
→Ɛ=1- = 0.8234580161 ~ 82. 3458161% (82% Efficiency for Old Steam Engine)
453.15 K
373.15 K
→Ɛ=1- = 0. 5893548132 ~ 58. 93548132% (59% Efficiency for Modern Steam
633.15 K
Engine)

10. The enthalpy of vaporization of Ethanol is 43.5 kJ mol-1 at its normal boiling point of 352
K. Calculate the entropy of vaporization of ethanol at this temperature and the entropy of
surroundings.
Given:
ΔHvap = 43. 5 kJ ~ 43500 J T =352 K
Solution:
 Δ H vap 43500 J
(a) ΔSvap = = = 123. 5795455 JK-1
T 352 K

(b) ΔSsys + ΔSsurr = 0 ; therefore ΔSsurr = -123. 5795455 JK-1

IV. Free Energy (Agacer)
1. The fugacity coefficient of a certain gas at 290 K and 2.1 MPa is 0.68. Calculate the
difference of its molar Gibbs energy from that of a perfect gas in the same state.
Given:
T = 298 K P = 2.1 MPa ~ 2.1×106 Pa φ = 0.68
 Solution:

Gо = Gөm + RTln ( pf ) (for perfect gas)

ө

= RTln( ), but
f f
thus; Gо - Gөm ө Θ = φ,
p p
Gо - Gөm = RTln(φ)
→ Gо - Gөm = (8.314 JK-1mol-1)(290 K)[ln(0.68)] = -929.855381 Jmol-1 ~ -0.929855381 kJmol-1

2. Derive the thermodynamic equation of state ( dHdP ) = V - T( dVdP )

T P
Solution:
H = U + PV (definition of enthalpy) → dH = dU + PdV + VdP
 but, dU = -PdV + TdS (from 1st Law), thus dH = PdV + VdP - PdV + TdS,
therefore; dH = VdP + TdS
→ dH = VdP + TdS

dH = VdP + TdS → ( dHdP ) = V + T ( dPdS )

T T

( dPdS ) = -( dVdT ) (from maxwell relations)

T P

( dHdP ) = V + T [ - ( dVdT ) ] → ( dHdP ) = V - T( dVdP )

T P T P

→( ) = V - T(
dP )
dH dV
dPT P

3. Suppose that 3.0 mmol N2(g) occupies 36 dm3 at 300 K and expands to 60 dm 3. Calculate
ΔG for the process.
Given:
 n = 3.0 mmol ~
V1 = 36 dm3 T = 298 K V2 = 60 dm3
0.003 mol
Solution:

Q = (-w) → dW = -PΔV = w = nRTln

( ) ( )
V1
V2
= -nRTln
P2
P1
(from 1st law)

thus, w = nRTln( )V1

V2

→ w = (0.003 mol)(8.314 JK mol )(298 K)[ln

-1 -1
( )
36 dm 3
60 dm 3
] = -3.796821787 J

ΔG = - w
→ ΔG = - (-3.796821787 J) = 3.796821787 J

4. Calculate the molar Gibbs energy of oxygen when its pressure is increased isothermally
from 50.0 kPa to 100.0 kPa at 500 K.
Given:
P1 = 50.0 kPa ~ 50000 Pa P2 = 100.0 kPa ~ 100000 Pa T = 500 K
Solution:

ΔGm = RTln ( )
P2
P1

[
→ ΔGm = (8.314 JK-1mol-1)(500 K) ln
50000 Pa )]
( 100000 Pa
= 2881.41283 Jmol -1
5. Show that, for a perfect gas, ( )
dU
dS V
= T and ( ) = -P
dU
dV S
Solution:
dU = TdS - PdV (fundamental property relation for internal energy)

( dUdS ) + ( dU
U = f (S, V) → dU =
VdV ) S

→ dU = ( ) +(
dV )
dU dU
dS V S

but, ( ) = -P and (
dS )
dU dU
=T
dV S V

[ dV dS ] [ dS dV ] dV
(
d dU
) =
V S
(
d dU
) →[
S V
d
( T ) ] = [ (−P ) ]
d
dSV
S
S
V

( dVdT ) = - ( dPdS )
S V
V. LIQUIDS (Matibag)

1. For liquid acetone at 20℃ and 1 bar:

α = 1.487 x 10−3 K−1, κ = 62 x 10−6 bar−1, ρ = 0.777 g − cm−3
a) What is the density of the liquid when its state is changed to 0℃ and 10 bar?
b) What is the pressure generated by heating at constant volume from 20℃ and
1 bar to 30℃ ?

Given:
α = 1.487 x 10−3 K−1 T 1=20 ℃ P2=10 ¯¿
κ = 62 x 10−6 bar−1 T 2=0 ℃
ρ = 0.777 g − cm−3 P1=1 ¯¿

P1
a. ln ( )=∝(T 2−T 1)−K (P2−P1 )
P2
2❑
0.777 g /c m
ln ( )=( 1.487 x 10−3 ℃−1 )(O℃−20 ℃)−(62 x 1 0−6 ba r−1 )¿
P2

P2=0.8009018061 g/c m3

b. V 1=V 2 , P1 =P 2
P
ln ( 1 )=¿ ∝=(T 2 −T 1 )−K (P2−P1 )
P2
(1.487 x 1 0−3 ℃−1)(30 ℃−20℃ )=(62 x 1 0−6 ba r −1) ¿

P2=240.8387 ¯¿
2. 5 kg of liquid carbon tetrachloride undergo a reversible isobaric change of state at 1 bar
during the temperature changes from 0℃ to 20℃ . Determine W, Q, ΔH, ΔU. The
properties of liquid CCl4 at 1 bar and 0℃ (can be assumed to be independent of
temperature) is as follows:

Given:
α = 1.2 x 10-3 K-1, Cp= 0.84 kJ kg-1 K-1, ρ = 1590 kg m-3

dV 1 1 m3 −4 m
3
=adT −kdPV 1= = =6.289 x 1 0
V P1 kg kg
dV M V2
=adT =ln ( )=a(T 2−T 1)→V 2=V 1 exp[a(T 2−T 1)]
V M V1
3
−4 −3 m −4
V 2=(6.289 x 1 0 )exp[1.2 x 1 0 (20−0)]=6.442 x 1 0
kg
Δv =m(V 2−V 1 )=5(6.442 x 1 0 −6.289 x 10 )=7.638 x 1 0−5 m3
−4 −4

W =−∫ PdV = -P Δv =−(10 5 Pa)¿

kj
ΔH =m C p (T 2−T 1)=5 kg(0.84 )(20−0) K=84 kj
kg−K

For constant P processes: Q= Δ H Q=84 kj

1 kj
ΔU =Q+W =84 kj+(−7.638 J )( )
1000 J

ΔU =83.9920 kJ
3. The time of flow of water through an Ostwald viscometer is 1.52 minutes. For the same
volume of an organic liquid of density 0.800 g/cm3, the time is 2.25 minutes. Find the
viscosity of the liquid relative to that of water in centipoise.

Given:

3
T 1=1.52 min P1=1.00 g /c m
3
T 2=2.25 min P 2=0.800 g/c m
μ=1cp

¿ viscometry equation
μ 1 p2 t 2
=
μ 2 p1 t 1

0.800 g /c m3 2.25 min

μ1=(1 cp)( 3
)( )
1.00 g /c m 1.52min

μ1=1.1842 cp
4. A steel ball of density 7.90 g/cm3 and 4-mm diameter requires 2.5 s to fall a distance of 1
m through a liquid of density 1.10 g/cm3.
a) Calculate the viscosity of the liquid in cP.
b) Calculate the amount of time in seconds that is required for the ball to cover the same
distance if it falls through water.

Given:
1m
ρ=7.90 g / c m
3
v= =0.4 m/s
2.5 s
ρm =1.10 g /c m3
4 mm
r= =2 mm
2

a. Using Stoke’s Law

2
2 r (ρ−ρm )g
μ= =2 ¿ ¿
qv

μ=148.24 cP
μ 2 (ρ−ρ m) t 2
b. =
μ 1 (ρ−ρ m) t 1

1 cP (7900 kg / m3 −1000 kg/m 3)t 2

=
148.24 cP (7900 kg /m3−1100 kg /m3 )(2.5 s)

t 2=0.016620 s
5. A 0.6-mm diameter glass tube is inserted into kerosene at 20℃ in a cup. The contact
angle of kerosene in the glass tube is measured to be 26.. The density of kerosene is 0.81
g/cm3. Determine the capillary rise of water in the tube.

Given:

0.6 mm g
r= =0.3 mm ρ=0.81 3
2 cm
o
ф=26.0

N
For kerosene σ =0.028
m

2σ
Using capillary rise equation → h= cosф
pgr

3
2(0.028 N /m) o 1 0 mm
h= cos 26. 0 ( )
kg m −3 1m
(810 3 )( 9.81 2 )(0.3 x 1 0 m)
m s

h=21.1114 mm
6. Consider a mixture of benzene and methylbenzene, which form an approximately ideal
solution, and suppose 1.0mol C6H6(l) is mixed with 2.0mol C6H5CH3(l).

Given:
x benzene=0.33 T =25 ℃
x methylbenzene =0.67 RT =2.48 kj mol
−1

Δ mix G/n=(2.48 kj mol −1 )(0.33 ln 0.33+0.67 ln0.67)

−1
Δ mix G/n=−1.6 kj mol

Δ mix S /n=−(8.314 J K −1 mo l−1)(0.33 ln 0.33+ 0.67 ln 0.67)

−1 −1
Δ mix S /n=5.3 J K mol
7. Identify the value of the parameter ξ that would be appropriate to model a mixture of
benzene and cyclohexane at 25°C, and estimate the Gibbs energy of mixing for an
equimolar mixture.

Given:
1
x a= x b=
2
e −1
H 701 mo l
ξ= =
RT x a x b (8.3145 J K −1 mo l−1 )(298 K)

ξ=1.13

1 1 1 1 −1
Δ mix G/n= RTln + RTln + 701 J mo l
2 2 2 2

Δ mix G/n=−1.02kJ mo l −1
VI. Phase Equilibrium (Matibag)

1. Write the phase-equilibrium conditions for a liquid solution of acetone and water in
equilibrium with its vapor and explain briefly.

- Liquid Composition ( x i) and vapor composition ( y i ) remain constant

Molar Gibbs free energy change for the system is ZERO. The Chemical potentials
and the partial fugacities are equal.

ΔG =0
T ,P
liquid vapour
uacetone =u acetone
liquid vapour
u water=u water
2. Nitrogen and hydrogen combine at a high temperature, in the presence of a catalyst, to
produce ammonia. N2(g)+3H2(g)⟶2NH3(g).Assume 0.130 mol N2 and 0.404 mol H2
are present initially. After complete reaction, how many moles of ammonia are produced?
NH3:______mol, How many moles of H2 remain? H2:____mol ,How many moles of N2
remain?, N2:____mol. What is the limiting reactant?

a. NH3 = 0.130 + 0.404 mol

= 0.534 moles

b. Total moles of H2 will remain -

2 moles NH3 requires ----------------> 3 moles H2

1 moles NH3 will require ----------------> 3/2 moles H2

0.534 moles NH3 will require ----------------> (3/2) * 0.534 moles H2

0.801 moles of H2

c. Total moles of N2 will remain -

2 moles NH3 requires ----------------> 1 moles N2

1 moles NH3 will require ----------------> 1/2 moles N2

0.534 moles NH3 will require ----------------> (1/2) * 0.534 moles N2

0.267 moles of N2

d. the limiting reactant will be nitrogen.

3. CH4(g) + 2O2(g) ↔ CO2(g) + 2H2O(g)

 a) Write the equilibrium expression for the reaction above.
b) Calculate the value of Keq given the following equilibrium conditions. Show all work.
CH4 = 0.10M O2 = 0.20M CO2 = 1.5M H2O = 3.0M

a. K e =[C O2]¿ ¿ b. K eq =(1.5 M )¿ ¿

K eq =3375

4. The normal boiling point of benzene is 80°C. The enthalpy of vaporization ∆Hvapor is
30.8 kJ/mol. Calculate the vaporpressure of benzene at 20°C.
 Given:
P1=1 atm ΔH vap=30.8 kj/mol
T 1=353.15 k T 2=293.15 k

d (lnP) ΔH vap
= 2
dT RT
P ΔH vap 1 1
ln ( 2 )= ( − )
P1 R❑
2
T 2 T 1

−ΔH vap 1 1
P2=P1 exp( ( − ))
R T2 T1
ρ P2=(1 atm)exp ¿

P2=0.11682 atm

5. What is the activity of liquid water at 100 bar and 25°C assuming the density of water is
taken as 1.00 g/cm3?
 Given:
P=100 ¯¿ ρ=1.00 g / c m3
T =298.15 K

V (P−P)
a=exp [ ]
RT
a=exp ¿

a=1.07460

6. Estimate the molar solubility of oxygen in water at 25°C and a partial pressure of 21 kPa,
the partial pressure of oxygen in the atmosphere at sea level. The Henry’s constant for
oxygen at 25°C is 7.9 x 104 kPa-kg/mol. The density of water at 25°Cis 0.99709 g/cm3.

Given:
 4
P02 =21 kPa❑ H 02=7.9 x 1 0 kPa−Kg/mol
P H 20=0.99704 g/c m3

From Henry’s Law:

P 02 21 kPa
P02 =m02 H 02−→m02= = =2.65822 x 1 0−4 mol 02 / Kg H 2 O
H 02 kPa−kg
7.9 x 1 0 4 3
m
−4 1 m3
[O2]=( 2.65822 x 1 0 )(997.09)( )
1000 L

−4
[O2]=2.65049 x 1 0 mol / L

7. A 50.00-mL sample of an aqueous solutions contains 1.08 g of human serum albumin, a

blood-plasma protein. The solution has an osmotic pressure of 5.85 mmHg at 298 K. What
is the molar mass of the albumin?

Given:
 V =50.00mL P=5.85 mmHg
msolute =1.08 g T =298 K

nsolute
π=[J ]RT = RT
V
1 atm 1L
( 5.85mmHg)( )(50.00 mL)( )
πV 760 mmHg 1000 mL
n solute= =
RT (0.08206 L−atm/ mol K )(298 K)
−5
n solute=1.57385 x 1 0 mol

1.08 g
M W solute = −5
1.57385 x 1 0 mol
M W solute =68621.3494 g /mol

8. The standard molar enthalpy of fusion of H2O is 6.02 kJ/mol. At 0°C, the density of ice
and liquid water are 0.9150 and 0.9999 g/mL, respectively. Estimate the melting
temperature of H2O (s) at 15 bar.

Given:
∆ H fus=6.02kj /mol T m=273.15 K ❑❑
 P=1 ¯¿ P H 20 (s)=0.9150 g /mL P H 20 (l )=0.9999 g/mL

1 1
Δ V fus =V H 20(l) −V H 20(s )= 3
−
(999.9 kg /m )(1000 g/1 kg)(1 mol/18.016 g) (915)(1000)( 1mol / 18.016 g)

−6 3
Δ V fus =−1.67182 x 10 m / mol

∆ H fus T 5 5 (6020 j/mol)

P=P+ lm( o )−−→15 x 1 0 Pa=1 x 1 0 Pa+ −6 3
ln ¿
∆ V fus T −1.67182 x 1 0 m /mol

T =273.04382 K
VII. Solutions and Colligative Properties (Tripon)

1. Find the molarity of all ions in a solution that contains 0.345 moles of aluminum chloride in
630 ml solution.
AlCl3

0.345 mol of AlCl 3 1 mole of Al 3

[Al3]= ( )
0.630 L 1 mole of AlCl 3
0.548
 Al3 +¿
mole ¿
L

0.345 mol of AlCl 3

[Cl-]= ¿
0.630 L
1.643
3 +¿
Al
mole ¿
L

2. Find the molarity of each ion present after mixing 15ml of 0.30 M HNO3 with 40 ml of 0.36 M
Ca(NO3)2. There is no reaction taking place.

a.)Find the number of moles HNO3

= M HNO 3 ¿ )
 0.30 mole
= (0.015 L)
L
= 4.5 x 10−3
b.)Find the number of moles Ca(NO3)2
= M Ca(NO3 )2 ¿)
0.36 mole
= (0.040 L)
L
= 1.4 x 10−2

−3 ¿
[H+] = 4.5 x 10 mol of H + 0.055 L ¿ =

0.08 M

−2
1.4 x 10 mol of Ca(NO 3)2
[Ca2+] = ¿=
0.055 L
0.25 M

The number of moles NO3- from HNO3

−3 −3
4.5 x 10 ¿= 4.5 x 10 mole NO3-
The number of moles NO3- from Ca(NO 3) 2
1.4 x 10−2 ¿ = 2.8 x 10−2mole NO3-

[NO3-] = ¿ ¿ =
0.59 M

3. A solution that contains 13.1 g of a nonvolatile solute in 300 g of benzene freezes at 4.2℃ . The
normal freezing point of benzene 5.5℃ . What is the molar mass of the solute? ( K F for benzene =
4.96℃ kg/mol

a.) T F = K F molality
 kg
1.3℃ = 4.96℃
mol
Mole
Molality = 0.262
kg

b.) The number of moles of solute

Mole
= 0.262 x 0.300 kg
kg
= 0.079 mole

c.) Molar Mass

13.1 g
=
0.079 mole
= 172 g/mol

4. Chloroform and methanol form an ideal solution. The solution boils at 15 °C and 0.145 atm .
At 30 °C , the vapor pressure of pure methanol is 0.100 atm and the vapor pressure of pure
chloroform is 0.233 atm. What is the mole fraction of chloroform in the solution?
 o o
PTotal =X methanol P methanol + X chloroform P chloroform
0.145 atm=X methanol (0.100 atm)+(1−X chloroform) 0.233 atm
0.145 atm=0.100 X methanol +0.233 atm−0.233 atm X methanol
0.233 atm X methanol −0.100 X methanol=0.233 atm−0.145 atm0.133 atm X methanol =0.088 atm
0.088 atm
X methanol= = 0.662
0.133 atm
X chloroform=1−0.662
X chloroform=¿ 0.338

5.) Calculate the freezing point of a 25.0 % by mass Na3PO4 solution. ( Kf for H2O = 2.01
°C .kg/mole)

25.0 g Na3PO4 ----------> 50 g H2O

 1mol of Na 3 PO 4
a.) 25.0 g Na3PO4( ) = 0.152 mole Na3PO4
164 g Na 3 PO 4
b.) Molality
0.152 mole Na3 PO 4
=( )
0.050 kg solvent
Mole
= 3.04
kg

Mole
ΔT Fp=4 ¿)(3.04 )
kg

ΔT Fp = -24.4 °C

6. Calculate the normal freezing point of a 0.6837 M aqueous solution of C12H22O11 that has a
density of 2.50 g/ml. ( C12H22O11 is a nonvolatile nondissociating solute.) The molal freezing
point depression constant of water is 1.86 °C .kg/mole

a.) change 0.6837 C12H22O11 into mass

342.2 g C 12 H 22 O11
0.6837 mole C 12 H 22O 11( )= 234.0 mole C12H22O11
1mole of C 12 H 22O 11
b.) Mass of solution
2.50 solution
1000 ml solution( )= 2500 g solution
1 ml solution
c.) Mass of H2O
= 2500 g solution - 234.0 solute
= 2266 g H2O
d.) Molality
0.6837 mole solute
=
2.500 kg H 2 O
Mole
= 0.2735
kg

T F = K F molality
°C Mole
= 1.86 kg (0.2735 )
mole kg
= -0.51 °C
T Fp=¿ -0.51 °C

7. Liquids A and B form an ideal solution. The vapor pressure of pure A is 0.900 atm at the
normal boiling point of a solution prepared from 0.300 mole of B and 0.756 mole of A. What is
 the vapor pressure of pure B at this temperature?

0.756 0.300 o
PTotal =P A + P B PTotal =X A P o A + X B P oB1 atm=
(0.900 atm)+ PB
0.300+0.756 0.300+0.756
1 atm=0.716(0.900 atm)+0.284 P B1 atm=0.644+0.284 P B1 atm=0.644+0.284 P B1 - 0.644 =
o o o

o
0.284 P B

0.365 = 0.284 Po B
o 0.365
P B=
0.284
o
P B= 1.29 atm

8. What is the molarity of an aqueous solution of C6H12O6 that has a normal boiling point of
103.14 °C and density of 1.21 g/ml? KB for water is 0.638 °C .kg/mole. ( C6H12O6 is a
nonvolatile nondissociating solute).

a.) T B = K B molality
 °C
1.40 = 0.638 kg
mole
1.40° C
kg mole solute
Molality = °C = 2.19
0.638 kg kg H 2O
mole
b.) change mole into mass
180 g C 6 H 12O 6
2.19 mole C6H12O6 ( ) = 394.2 g C6H12O6
1mole of C 6 H 12 O 6
c.) Find mass of solution
394.2 g C6H12O6 + 1000 g H2O = 1394.2 g solution
d.) Find volume of solution
1 ml solution
1394.2 g solution ( )= 1152 g solution
1.21 g solution
e.) Molality
2.19 mole C 6 H 12O 6
=
1.152 L
= 1.90 mol/L

9. The vapor pressure of pure benzene (C6H6) is 100. torr at 23.4. Calculate the vapor pressure of
a solution containing 27.8g of camphor (C10H16O) dissolved in 200. mL of benzene. The density
of benzene is 0.877 g/mL.
 X bcn=nben +n camn ben=200 ml(0.877 g /ml)¿ ) = 2.25 mol
1 mol
n cam=¿27.8 g ( ) = 0.183 mol
152.2
X ben=2.25 mol/(2.25 mol+0.183 mol)=0.925 mol
Pben=(X ben)¿
= 92.5 torr

10. Ethylene glycol (EG), CH2(OH)CH2(OH), is a common automobile antifreeze. Calculate the
freezing point of a solution containing 455 g of EG in 2692 g of water. Would you keep the
substance in your car radiator during the summer? The molar mass of EG is 62.01 g/mol. Kf =
1.86°C/m and Kb = 0.52°C for water.
Mol of Ethylene glycol
1mol of EG
455( ¿=7.34 mol
62.01
Molality of the solution
7.34 mol Ethylene glycol
= 2.73 M
2.692 kg of H 2 O
ΔT = K f m=(1.86 ° C/m)(2.73 M )
= 5.08
°C

Since pure water freezes at 0°C, the solution will freeze at -5.08°C

The boiling point elevation can be calculated in the same way

ΔT = K b m=(0.52° C /m)(2.73 M )
= 1.53° C

11. The freezing point of a glucose solution (C6H12O6 has a molar mass of 180.0 g/mol) is =
12.5° C . The density of the solution is 2.05 g/mol. What is the molarity of the glucose solution? (
K f for water is 1.86 ° C kg/mol).
ΔT fp = K fp molality
Mole
12.5° C = 1.86° C (molality)
kg
12.5 °C
Mole
Molality = Mole = 6.72
1.86° C kg
kg

Mass of solute
Mole 180.0 g glucose
6.72 ( ¿ 1209.6 g glucose
kg 1mole of glucose

Mass of solution
1000 g H2O + 1209.6 g glucose = 2209.6 g solution

Volume of solution
1ml solution
2209.6 g solution( ) = 1078 ml solution ⇒ 1.078 L solution
2.05 g /mol
Molality
6.72mole glucose
=
1.078 L solution
= 6.23 mole/L
VIII. Phase Diagrams of Liquid Vapor (Tripon)
1. The densities of ice and water at 273K and 1 atm are 0.917 g cm-3 and 0.9998 g
cm-3, respectively. The molar heat of fusion of ice is 6010 J mol-1. Calculate the
change in melting point if the pressure is changed to 70 atm.

P2 T2
dP ΔH Fusion ΔH Fusion ΔH Fusion T 2 dT
= ⇒ ∫ ❑dP ∫ ❑ = ∫❑ T
dT T ΔV Fusion P 1 T1 T ΔV Fusion ΔV Fusion T 1
ΔH Fusion T 2
∴ P 2−P 1=70 atm−1 atm=69 atm= ln( )
ΔV Fusion T 1
❑
❑ 1 1 1 1
ΔV ❑ ¿
fusion❑ ❑ V ❑liquid −V ❑solid = ❑ −¿❑❑ ❑ = − ¿
P❑liquid ❑ P❑solid lgm/cc 0.917 gm /cc ❑
= lgm/cc-1.901 gm/cc = 0.091 cc/gm

❑
Δ H ❑fusion❑ ¿❑ 6010 J /mol=333.9 J /gm ❑
ΔH Fusion T 2 (69 atm)(−0.091cc / gm) T2
69 atm = ln( )⇒ = ln( ¿
ΔV Fusion T 1 333.9 J /gm 273.15
T2 (99 atm)(101 J / L atm)(1 L/ 1000 cc)(−0.091 cc / gm)
ln( ¿= = -0.00137
273.15 333.9 J /gm
T 2= T 1 e−0.00137 = (273.15)(0.999)

=272.8 K
2. The normal boiling point of ethanol is 351.4K and at this temperature ∆Hvap=40.2kJ/mole. To
what value must the vapor pressure be reduced in order to boil ethanol at T=278K in a vacuum
distillation? Assume the enthalpy of vaporization is constant between 278K and 351.4K.

P2 Δ H vap 1 1
ln( ¿= ( − ¿
P1 R T1 T 2
40,200 J /mol 1 1
= ( − )
8.314 J /mol K 351.4 K 278 K
= (4835)(0.00285-0.00335)
= -2.4175
−2.4175
∴ P2=(1 atm) e
= 0.0891 atm

t/ °C P A / ¯¿ PB / ¯¿

-20.0 3.360 0.678

-30.0 2.380 0.441

-40.0 1.633 0.275

Saturation vapor pressures of propane (A) and n-butane (B)
3. The standard boiling point of propane is -41.8°C and that of n-butane is -0.2°C. Based on the
table for the lists vapor pressure data for the pure liquids. Assume that the liquid mixtures obey
Raoult’s law.

❑
a.) Calculate the compositions, x a❑, of the liquid mixtures with boiling points of -20.0°C, -30.0°C,
and -40.0°C at a pressure of 1 bar

P−Pb
X a=¿ ❑
Pa−Pb❑❑

At -20°C: X a= 0.120
At -30°C: X a= 0.288
At -40°C: X a= 0.534

b.) Calculate the compositions, yA, of the equilibrium vapor at these three temperatures
❑ ❑
y a= xa Pa / P

At -20°C: y a= 0.403
At -30°C: y a= 0.686
At -40°C: y a= 0.872

Temperature–composition phase diagram for the binary system of water (A) and phenol (B) at 1
bar. Only liquid phases are present.

4. Temperature–composition phase diagram for the binary system of water (A) and phenol (B) at
1 bar. These liquids are partially miscible below 67°C. Phenol is more dense than water, so the
layer with the higher mole fraction of phenol is the bottom layer. Suppose you place 4.0 mol of
H2O and 1.0 mol of phenol in a beaker at 30°C and gently stir to allow the layers to equilibrate.

a.) What are the compositions of the equilibrated top and bottom layers?
The system point is at z B = .1/0 mol/= (5.0 mol)= 0:20 and t = 30°C, in the two-phase
area. The ends of the tie line through this point give the compositions x B (top) = 0.02
And x B (bottom) = 0.31.

b.) Find the amount of each component in the bottom layer.

n(bottom) 0.20−0.02
= = 1.6
n(top) 0.31−0.20

Solve simultaneously with n(bottom)+n(top) =5.0 mol to get n(bottom) = 3.1 mol.
Then, in the bottom layer we have

n B= x B n = .0.31/.3.1 mol/ = 1.0 mol n A =¿ 3.1 mol -1.0 mol = 2.1 mol

c.) As you gradually stir more phenol into the beaker, maintaining the temperature at 30°C,
what changes occur in the volumes and compositions of the two layers? Assuming that
one layer eventually disappears, what additional amount of phenol is needed to cause this
to happen?

The volume of the bottom layer increases and that of the top layer decreases. There is no
change in the compositions of the two phases. When the overall system composition
reaches z b=0.31 , the top layer disappears; the amount of phenol in the system at this
point is calculated from

nB
z B=
n A + nB ❑
z n (0.31)(4.0 mol)
n B= B A =
1−z B 1−0.31
= 1.8 mol
References:
● Engel, T., & Reid, P. (2012), Physical Chemistry, Pearson. Levine, I.N. (2009), Physical

Chemistry, McGraw-Hill.

● James Keeler, Julio de Paula, and Peter Atkins: Atkins' Physical Chemistry