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PHYSICAL CHEMISTRY 1
Lecturer: Dr. Eng. Nguyễn Quang Long
CC05 – Group 02
Team member
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
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
t c t c c c
mi + mi =mf +mf ⇒ 7.376 +0.292=1.352+ mf ⇒ mf =6.316 kg
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
=
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
√
ni 1 1
( 1−x ) 1.1− x 6.2− x
2 2
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)
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.
(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.