VIET NAM NATIONAL UNIVERSITY

HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGNEERING

Report Assignment

PHYSICAL CHEMISTRY 1
Lecturer: Dr. Eng. Nguyễn Quang Long

CC05 – Group 02

Team member

No. Name Student ID Sign

1 Nguyễn Tấn Phát 2153679

2 Đồng Hữu Minh Nhật 2153651

3 Lý Phổ Phương 2153710

4 Nguyễn Anh Quân 2153741

5 Võ Đăng Hoàng Vũ 2153982

Ho Chi Minh, Friday 16th December 2022

Question 1:

A rigid tank of volume V= 0.51 m3 is connected to a piston-cylinder assembly

by a valve, as shown below. Both vessels contain pure water. They are immersed in
a constant-temperature bath at Tb= 230oC and P= 600kPa. Consider the tank and
the piston–cylinder assembly as the system and the constant temperature bath as
the surroundings. Initially, the valve is closed and both units are in equilibrium with
the surroundings (the bath). The rigid tank contains saturated water with a quality of
95% (i.e., 95% of the mass of water is vapor). The piston-cylinder assembly initially
has a volume of Vinitial= 0.11 m3.

The valve is then opened. The water flows into the piston–cylinder until
equilibrium is obtained. For this process, determine the work done, W, by the piston;
the change in internal energy, U, of the system; and the heat transferred, Q.
Solution
 At initial phase

t 0
Consider rigid tank under equilibrium with surrounding T i=230 C∧quality ( xi ) =95 % ,
using table A-4 from Appendices, we get
 ( )
3
t m
Specific volume , v i=0.001209+0.95 ×0.071505=0.069139
kg

Initial entropy , sti =2.6100+0.95 ×3.6028=6.0327 ( kgkJ. K )

Initial internal energy ,u ti=986.76+0.95 ×1616.1=2522.055 ( kJkg )
t Vt 0.51
Mass of water initial in tank, mi = t
= =7.376 kg
v i
0.069139

Consider piston-cylinder under equilibrium with surrounding

t 0
T i=230 C∧quality ( xi ) =95 % , using table A-6 from Appendices and interpolation
t

method we get Internal energy

2639.4−ui
2721.2−u
t
i
=
( 200+273 )−( 230+273 )
( 250+273 )−( 230+273 )
t
⇒ ui =2688.5
kJ
kg ( )
( )
c 3
0.35212−v i
( 200+273 )− (230 +273 ) c m
Specific volume c
= ⇒ v i =0.37719
0.39390−v i ( 250+273 )− (230 +273 ) kg

c
Entropy
6.9683−s i
7.1833−s
c
i
=
( 200+273 )−( 230+273 )
( 250+273 )−( 230+273 )
c
⇒ si =7.0973
kJ
kg . K ( )
c
c Vi 0.11
Mass of H 2 O∈cylinder m = i c
= =0.292 k g
v i
0.37719

 At final phase

Under final equilibrium after valve is opened. Both system and surrounding will be in
equilibrium Ptf =Pcf =600 kPaT tf =T cf =230o C

( ) ( )
3
m kJ
Consider tank at superheated state v tf =0.37719 t
, s f =7.0973
kg kg . K

t Vt 0.51
⇒ mass of H2O in tank is mf = t
= =1.352 kg
v f
0.37719

Using mass balance of system:

t c t c c c
mi + mi =mf +mf ⇒ 7.376 +0.292=1.352+ mf ⇒ mf =6.316 kg

⇒ total volume of piston cylinder v cf =mcf × v cf =6.316 × v ci =6.316 × 0.37719=2.38 m3

⇒ the work done, W, by the piston is ∆ W =P × ( v cf −v ci ) =600 × (2.38−0.11 )=1362 kJ

⇒ the change in internal energy

∆ U sys=U f −U i=( mcf ×ucf +mtf ×u tf ) −( mic ×uci +mti ×u ti ) =( 6.316 ×2688.5+1.352 ×2688.5 )−( 0.292 ×2688.5+7.3

Using 1st law the heat transferred ∆ Q=∆ U + ∆ W =1227.69832+1362=2589.69832 kJ

Question 2:
One step in the manufacture of sulfuric acid is the oxidation of sulfur dioxide to sulfur
trioxide. Consider performing this oxidation at a pressure of P= 1.1 atm with molar
ratio SO2:O2 = 1:1.1, using air as the oxygen source (assuming air contains 21%O 2
and 79% N2 only). The reactor temperature is maintained at a constant temperature
of T= 650°C.
(a) What is the equilibrium constant (KP) at processing conditions?
(b) If equilibrium is attained within the reactor, what is the exit stream composition?
(c) How much heat must be supplied to or removed from the reactor to maintain
isothermal operation?
(d) Plot the equilibrium conversion of SO2 (the extent of reaction) as a function of
operation pressure (P= 1 – 20 atm) and comment about the chart.
(e) Plot the KP; KC; Kx; Kn as a function of operation pressure
(P= 1 – 20 atm) and comment about the chart.
Solution
1
Reaction: S O2+ O2 → S O3
2
a) Information from handbook
° kJ °
∆ H (SO ) =−296 , 83 , ∆ H (SO ) =−395 ,72 kJ /mol ,
2
mol 3

° °
∆ H (O )=0 kJ /mol ⇒ H (25 ℃)=−98 , 89 kJ /mol
2

J J
∆ C p (S O ,25 ℃)=39 , 87 ), ∆ C p (S O ,25 ℃)=50 ,67 J /(K .mol ), ∆ C p (O , 25℃ )=29,355
2
K . mol 3 2
K . mol
1 J
⇒ ∆ C p (25 ℃) =50 ,67 – 39 , 87 – ( 29.355 ) =−3,8775
2 K . mol
° ° kJ ° kJ ° kJ
∆ G( SO )=−300 , 19 kJ / mol, ∆ G( SO )=−371 , 06 , ∆ G( O )=0 ⇒ ∆ G(25 ℃)=−70 ,87
2 3
mol 2
mol mol
Apply Gibbs – Helmholtz equation
∆ G°(650 ℃) ∆ G°(25 ℃ ) 923
( )
T
dT
− ∫ ∆ H ( 25℃ )+ ∫ ∆C p (25 ℃) dT 2
°
=
923 298 298 298 T

∆G °(650℃ ) −70 , 87 923 −97 , 73 3,8775

⇔ = −∫ ( − )dT
923 298 298 T2 1000 T

∆G °(650℃ ) −70 , 87
⇔
923
=
298
−97 , 73.
1
−
1
923 298
+
3,8775
1000 (
. ln(
923
298
) )
°
−∆ G( 650℃ ) −−10 ,5. 1000
° kJ RT 8,314.923
⇔∆G ( 650 ℃) =−10.5 ⇒ K p=e =e =3.93
mol

1 −1
b) Basic O2=1 , 1mol ; SO2=1 mol ⇒ nN =4 ,1 mol , ⅀ n=6 , 2− x , ∆ n=
2 22

1
State S O2 O S O3
2 2
Initial 1 1.1 0
1
Reaction x x x
2
1
Equilibrium 1−x 1.1− x x
2
We have
Kp x
K n= ⇒ .¿

(∑ ) √
∆n
P 1
( 1− x ) . 1 , 1− x
ni 2

{ {
0.7985 mol O2 13.54 % O2
0.603 mol S O3 10.22 % S O3
⇒ The exit stream is at mole fraction we have
0.397 mol S O2 6.7 % S O2
4.1 mol N 2 69.54 % N 2

c) The heat supplied will be equal the heat of reaction at this temperature so, the
heat that is
923
−3,8775 kJ
+ ∫ ∆ C p dT =−98 , 89+
° °
∆H ( 650℃ ) =∆ H ( 25℃ ) . ( 923−298 )=−101 , 31
298 1000 mol

d) Because at b) we chose the basic is 1 mole S O2 so the conversion of S O2 equal

the mole of S O2 reacted in this reaction
0.603
α SO = =0.603=x
2
1
We have the relation between the mole S O2 reacted and the operation pressure
 (∑ ) ( )
∆n −1
P x P
K P=K n × ⇒ 3.93= × 2

√
ni 1 1
( 1−x ) 1.1− x 6.2− x
2 2

We increase the pressure from 1 to 20 atm, we get value of x:

P
1 2 3 4 5 6 7 8 9 10
(atm)
x
0.592 0.668 0.709 0.736 0.756 0.771 0.784 0.795 0.804 0.811
(mole)
P
11 12 13 14 15 16 17 18 19 20
(atm)
x
0.818 0.824 0.830 0.835 0.839 0.843 0.847 0.851 0.854 0.857
(mole)

Graph
25

20

15
P (atm)

10

0
0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9
x=α (mole)

e) Because K P∧K C is only depend on temperature, the increasing of pressure

doesn’t affect to K P∧K C
Kp 3 , 93
K c= ∆n
= −1
=34 .19
( RT ) 2
( 0,082.923 )
With K n, for each pressure value, the number of moles of reactants and products at
equilibrium as well as the total number of moles will change, so we will take the
x
K n=
value of x in d) to calculate K n. 1
( 1−x ) 1.1− x
2 √
P
1 2 3 4 5 6 7 8 9 10
(atm)
x
0.592 0.668 0.709 0.736 0.756 0.771 0.784 0.795 0.804 0.811
(mole)

Kn 1.62 2.30 2.82 3.26 3.65 3.98 4.31 4.63 4.91 5.15

P
11 12 13 14 15 16 17 18 19 20
(atm)
 x
0.818 0.824 0.830 0.835 0.839 0.843 0.847 0.851 0.854 0.857
(mole)

Kn 5.41 5.64 5.90 6.13 6.32 6.52 6.73 6.95 7.13 7.31

Graph
25

20

15
P (atm)

10

0
1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00

Kn

Kp
And we have K x = −1
=3.93 × √ P
2
P
P
1 2 3 4 5 6 7 8 9 10
(atm)
Kx 3.93 5.56 6.81 7.86 8.79 9.63 10.40 11.12 11.79 12.43
P
11 12 13 14 15 16 17 18 19 20
(atm)
Kx 13.03 13.61 14.17 14.70 15.22 15.72 16.20 16.67 17.13 17.58

Graph
25

20

15
P (atm)

10

0
2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00 18.00 20.00
Kx

Question 2:
For the system water (1) plus ethyl acetate (2) plus acetone (3) at 30°C and 1 atm,
mole-fraction compositions of pairs of liquid phases  and  in equilibrium are
presented as followings where the last set of data gives the isothermal critical
solution point.

(a) Plot the ternary phase diagram including tie lines;

(b) Suppose 0.20 mole of acetone, 0.25 mole of ethyl acetate, and 0.25 mole of
water are mixed at 30°C and 1 atm. Show the system in the diagram. If the system is
heterogeneous, find the mass of each component present in each phase at
equilibrium.

Solution

We use excel to draw this ternary plot and after we drawn it, the sysetem 0.20 mol of
acetone, 0.25 mole of ethyl acetat, and 0.25 mole of water is homogenous.