15 Mixing and Solution

SKF 2123 - Energy Balance
Instructor: Dr Azeman Mustafa

Balances on Nonreactive Processes
JKG- FKKKSA
Page 8 - 1
Mixing and Solution
When two different liquids are mixed or when a gas or solid is
dissolved into a liquid, bonds are broken between neighboring
molecules.
Net release in energy will result when the bonds are broken and
solution is form.
Suppose we mix 1 mol of pure liquid of sulfuric acid with water at
specified temperature and pressure
The energy balance for this constant pressure-process is given by:
The pure solute and solvent at the same T and P is the Heat of
Solution at that temperature and pressure.
( )
O H l SO H aq SO H
H H H H Q
2 4 2 4 2
) ( ) (
+ = =
JKG- FKKKSA
Page 8 - 2
Heat of Mixing and Solutions
Heats of solution,
s
(T,r) - enthalpy change when 1 mol of solute (gas or
solid) is dissolved in r moles of a liquid solvent at constant temperature T
MgSO4 added to water has H
soln
= -91.2 kJ/mol.
NH
4
NO
3
added to water has H
soln
= + 26.4 kJ/mol.
MgSO4 is used in hot packs and NH
4
NO
3
is used in cold packs
H
soln
is positive for endothermic (heat absorbing) processes and negative
for exothermic (heat generating) processes
Dissolution can be spontaneous in either case
Usually exothermic for salts with small, very positive cations (high H
hyd
)
CaCl
2
, -82.8 kJ/mol
KCl, +17.2 kJ/mol
JKG- FKKKSA
Page 8 - 3
Heats of mixing,
m
(T,r) - enthalpy change when 1 mol of liquid solute is
mixed with r moles of a liquid solvent at constant temperature T
Enthalpy of a solution (or mixing) containing r moles H
2
O/mole solute for
reference states of pure solute and solvent at 25
o
C and 1 atm is
and for reference states of pure solvent and an infinitely dilute solution at
25
o
C and 1 atm
( ) r H H
s

=

=
n as H H hence
) ( H - (r) H H
s
s s

JKG- FKKKSA
Page 8 - 4
Heats of solution or mixing for an ideal mixture / solution (e.g. gas mixtures
or liquid mixtures of structurally similar compounds, e.g. Paraffins,
aromatics) is usually negligible, the enthalpy of mixtures is approximately
Aqueous solution of strong acids or bases of certain gases (HCl) or solids
(NaOH) heats of solution should be included in energy balance calculations
Data of the heats of solution is given in Perrys Chemical Engineering
Handbook on pp 2-201- 2-204.
Some values of the heat of solution at 25
o
C of HCl(g) and NaOH (s) and the
heat of mixing at 25
o
C of H
2
SO
4
(l) are given in Table B.11, p.653.
i i mix
H n H

JKG- FKKKSA
Page 8 - 5
The heat of solution
and mixing of
HCl(g) and NaOH
(s) and the heat of
mixing at 25
o
C of
H
2
SO
4
(l)
JKG- FKKKSA
Page 8 - 6
Example 17 - Prob. 8.82
Use table B-11 to determine the specific enthalpy (kJ/mol HCl) of
hydrochloric acid containing 1 mol HCl/5 mol H
2
O at 25
o
C relative to ;
i. HCl(g) and H
2
O(l) at 25
o
C
ii. H
2
O(l) and an infinitely dilute HCl solution at 25
o
C
HCl mol
kJ
-64.05 5) (r H 11; - B Table

HCl mol 1
O H 5mol
r
s
2
= =
=
( )
HCl mol
kJ
11.09 75.14 64.05 ) ( H - 5) (r H H
mol
kJ
75.14 - ) ( H and
mol
kJ
64.05 - 5) (r H ; 11 - B Table
s s
s s
+ = = = =
= = =

JKG- FKKKSA
Page 8 - 7
Sodium hydroxide (NaOH) is dissolved in enough water to make up a
20% mole % solution. If the NaOH and water were initially at 77
o
F
(25
o
C), how much heat (Btu/Ibm solution) must be removed for the
solution to be at 77
o
F. Assume the process is carried out at
constant pressure. Use table B-11 to evaluate
s
20 mole % NaOH (aq)
25
o
C
H
2
O(l)
25
o
C
NaOH (s)
25
o
C Mixing
tank
JKG- FKKKSA
Page 8 - 8
Basis : 100 moles of 20% mole NaOH solution
( 20 moles NaOH(s), 80 moles H2O (l)) both at 25
o
C
Thus, Heat must be removed to keep the solution at 25
o
C
NaOH mol
kJ
-34.43 4) (r H 11; - B Table
4
NaOH mol 20
O H mol 80
r
s
2
= =
= =

JKG- FKKKSA
Page 8 - 9
Since the inlet temperature of both substances is 25
o
C (i.e. ref. state) the
corresponding enthalpies are zero
( )
( )
Ibm
BTU
132.5 removed
solution Ibm
BTU
Heat
Ibm 4.928
1000g
Ibm 2.2

O H mol
O H g 18
x
solution mol
O H mol 0.8
NaOH mol
NaOH g 40
x
solution mol
NaOH mol 0.2
solution moles 100 solution Ibm
BTU 653
J
BTU 9.486x10
kJ
1000J
NaOH mol
kJ
34.43 - NaOH moles 20 4) ( H H Q
H n H n Q
2
2 2
4
s
out in
in in out out
= |
.
|
\
|
=
|
|
.
|
\
|
(
|
|
.
|
\
|
+ |
.
|
\
|
=
=
|
|
.
|
\
|
|
.
|
\
|
|
.
|
\
|
= = = =
=
n

NaOH NaOH
-34.43 kJ/mol
NaOH
100
0
0
20
80
NaOH(s), 25
o
C
H
2
O(l), 25
o
C
NaOH(aq), 25
o
C
H
out
(kJ/mol) n
out
(mol) H
in
(kJ/mol) n
in
(mol) Substance
JKG- FKKKSA
Page 8 - 10
Example 18 - Heat of mixing (H
2
SO
4
solution)
What is the specific enthalpy of 80 wt % H
2
SO
4
(aq, 110
o
F) relative to
pure H
2
SO
4
at (77
o
F) and pure water at 32
o
F.
Basis : 1 lbm of 80 wt % H
2
SO
4
(aq, 110
o
F)
( 0.8 lbm H
2
SO
4
(l),77
o
F ; 0.2 lbm H2O (l),32
o
F)
0.8 lbm H
2
SO
4
(l),77
o
F
1 lbm of 80 wt % H
2
SO
4
(aq, 110
o
F)
0.2 lbm H2O (l),32
o
F
JKG- FKKKSA
Page 8 - 11
Solution to Example 18 Manually
calculated
( ) BTU 121.2 -
kJ 10
BTU 10 x 9.486
SO H lbm 0.8
2.2lbm
1000g

SO H 98g
SO H mol

SO H mol
kJ
34.43 - 1.36) (r H 11; - B Table
1.36
SO H
lbm 98
mol
x lbm 0.8
O H
lbm 18
mol
x lbm 0.2
r
3 -
4 -
4 2
4 2
4 2
4 2
s
4 2
2
=
|
|
.
|
\
|
|
.
|
\
|
|
|
.
|
\
|
|
|
.
|
\
|
=
|
.
|
\
|
|
.
|
\
|
=
Pure H
2
O (l), 32
o
F
80 wt% H
2
SO
4
(l), 77
o
F
s
H
2
H
H
1
Pure H
2
SO
4
(l), 77
o
F
Pure H
2
O (l), 77
o
F
80 wt% H
2
SO
4
(l), 110
o
F
( ) ( ) BTU 9.0 F 32 - 77
F lbm-
BTU
1.0 O H lbm 0.2 dT C lbm 0.2 H
o
o 2
F 77
F 32
O H p, 1
o
o 2
= |
.
|
\
|
= =
(Hypothetical heating, cooling & isothermal mixing steps)

H Q =
JKG- FKKKSA
Page 8 - 12
( )
( )
( ) BTU 16.51
lbm 1
BTU
9.91 6.6 lbm 1 H
F lbm-
BTU
0.00038T 0.34
0.8 0.2
0.8

F lbm-
BTU
1
0.8 0.2
0.2

) conversion unit (require 2 B e ......Tabl
C y C y C y C
dT C lbm 1 H
2
o o
p, SO H p, O H
i
i p, i (aq) SO H p,
F 110
F 77
(aq) SO H wt%, 80
p 2
4
SO
2
H 4 2 O
2
H 2 4 2
o
o
4 2
= |
.
|
\
|
+ =
+ |
.
|
\
|
+
+ |
.
|
\
|
|
.
|
\
|
+
=
+ = =
=
( )
lbm
BTU
95.7
solution lbm 1
BTU 16.51 121.2 9

solution lbm 1
H H H
H
2 s 1
=
+
=
+ +
=
Note : Heat capacity for the solution (or dilute solution can be reasonably estimated
using the heat capacity of the pure solvent
JKG- FKKKSA
Page 8 - 13
H
2
SO
4
-H
2
O Enthalpy-Concentration Diagram
Table B-11 gives heat of mixing for aqueous sulfuric acid, and heats of
solutions for aqueous solutions of hydrochloride and sodium hydroxide at
25
o
C and 1 atm
Fig. 8.5-1, p. 399, is an enthalpy-concentration chart for a binary system
involving liquid mixtures of sulfuric acid (ref. states; 77
o
F (25
o
C) & 1 atm
and water (ref. states; 32
o
F (0
o
C) . It
is equivalent to heat of mixing or heat of solution data
can be used to solve energy balance problems for mixing or separation
of aqueous sulfuric acid streams
JKG- FKKKSA
Page 8 - 14
H
2
SO
4
-H
2
O Enthalpy-
Concentration Diagram
Reference states
H
2
SO
4
(l), 77
o
F (25
o
C) & 1 atm
H
2
O (l), 32
o
F (0
o
C)
JKG- FKKKSA
Page 8 - 15
H
2
SO
4
-H
2
An H x chart for aqueous solutions of
sulfuric acid at several temperatures.
How to read the figure:
What is the specific enthalpy (BTU/lb
m
)
of a 40 wt% sulfuric acid solution at
120
o
F?
From the figure the reading is about 55
Btu/lb
m
.
JKG- FKKKSA
Page 8 - 16
Solution to example 18 using H
2
SO
4
-H
2
O Enthalpy-
Concentration Diagram (Fig. 8.5-1)
Locate mass fraction
of H
2
SO
4
~ 0.8 (x-axis), move
vertically to ~ 110
o
F line and
then move horizontally
to estimate H (y-axis), hence
H~ - 96 BTU/lbm
JKG- FKKKSA
Page 8 - 17
Adiabatic Mixing
Adiabatic mixing is considered to have taken place if substances are mixed
in a well-insulated system, thus assuming no heat loss to its surrounding (i.e.
Q = 0). This is the condition in which the maximum temperature the product
solution can achieve.
The concentration of product solution can be estimated as follows;
JKG- FKKKSA
Page 8 - 18
Example 19 - Adiabatic Mixing
Pure water at 32
o
F is used to dilute 100 mL of 90% wt
H
2
SO
4
(aq, 32
o
F) in a well-insulated flask. Estimate the maximum
temperature the product solution can achieve, the concentration
of sulfuric acid (wt %), the specific enthalpy of this solution .
Water (32
o
F)
90 wt% H
2
SO
4
(32
o
F)
? wt% H
2
SO
4
(?
o
F)
Q = 0
JKG- FKKKSA
Page 8 - 19
Example 19 - Adiabatic Mixing
From Fig. 8.5-1 ;
The maximum temp.
~190
o
F, the corresponding
concentration ~ 65 wt%
H
2
SO
4
solution and the
specific enthalpy ~ - 66
BTU/lbm
190
o
F
JKG- FKKKSA
Page 8 - 20
Working session 16- Problem 8.95 (Modified)
An aqueous solution containing 85% wt H
2
SO
4
at 60
o
F (specific gravity = 1.78) is diluted
with pure liquid water at the same temperature. The feed solution volume is 350 mL.
The mixing may be considered adiabatic and the pressure is constant at 1 atm.
a. The product solution is to contain 30% wt H
2
SO
4
. Calculate the volume (mL) of the
water needed for dilution.
b. Use Fig. 8.5-1 to estimate the specific enthalpies (BTU/lbm) of the feed solution and
the water & calculate the enthalpy of the product solution and as well as the product
temperature
c. Use Fig. 8.5-1, estimate the maximum concentration (wt %) of the product solution and
temperature of the product solution that could be achieved by mixing pure water with a
350 mL of 85 wt% H
2
SO
4
solution (both at 60
o
F). How much water is needed.
d. How much heat (BTU) must be removed from the product solution calculated
in part (c) to keep its final temperature in part (c) at 77
o
F?
JKG- FKKKSA
Page 8 - 21
85% wt H
2
SO
4
(aq),60
o
F m
1
kg m
2
kg
350 mL 30 wt % H
2
SO
4
(aq, T
o
F)
H2O (l),60
o
F m
w
kg
a. The product solution is to contain 30% wt H
2
SO
4
. Calculate the volume (mL)
of the water needed for dilution.
( )
( ) mL 1142
L
mL 1000

kg 1
L
kg 1.142 ~ needed water pure of Volume
1.142kg m and kg 1.765 m then , kg 0.623 0.35L
L
kg
1.78 m Given
0.7m m 0.15m : bal. mass O H and 0.3m 0.85m : bal. mass SO H
w 2 1
2 w 1 2 2 1 4 2
= |
.
|
\
|
|
|
.
|
\
|
= = = |
.
|
\
|
=
= + =
JKG- FKKKSA
Page 8 - 22
b. Use Fig. 8.5-1 to estimate the specific enthalpies (BTU/lbm) of the feed
solution and the water & calculate the enthalpy of the product solution and
as well as the product temperature
( )
lbm
BTU
18.39 - F) T (aq, H and
lbm
BTU
27.5
kg
lbm 2.2
x kg 1.142
lbm
BTU
102.5 -
kg
lbm 2.2
x kg 0.623 F) T (aq, H
kg
2.2lbm
x 1.765kg Then
0 H m - H m Q : mixing adiabatic for balance Energy
lbm
BTU
27.5 F) 60 (l, H
lbm
BTU
102.5 - F) 60 (aq, H
solution feed of enthalpies Specific
o
SO H wt% 30
o
SO H wt% 30
out in
i i i i
o
O H
o
SO H wt% 85
4 2
4 2
2 4 2
=
|
.
|
\
|
|
.
|
\
|
+
|
.
|
\
|
|
.
|
\
|
= |
.
|
\
|
= =
= =

From Fig. 8.5-1, at 30 wt % H
2
SO
4
& H ~ - 18. 4 BTU/lbm, the product
temperature is about 130
o
F
JKG- FKKKSA
Page 8 - 23
Alternatively, the enthalpy
of the product solution
containing 30% wt H
2
SO
4
and as well as the product
temperature can be
estimated directly from
From Fig. 8.5-1 ;
The specific enthalpy ~ -
19 BTU/lbm, the product
temp. ~130
o
F
~ 130
o
F
JKG- FKKKSA
Page 8 - 24
c. Use Fig. 8.5-1, estimate the
maximum temperature of the
product solution that could be
achieved by mixing pure water
with a 350 mL of 85 wt%
H
2
SO
4
solution (both at 60
o
F)
and the concentration (wt %)
of the product solution. How
much water is needed?
From Fig. 8.5-1 : The maximum
temp. ~ 180
o
F, the
corresponding concentration ~
60 wt% H
2
SO
4
solution and
the specific enthalpy ~ - 64
BTU/lbm
JKG- FKKKSA
Page 8 - 25
Volume of pure water needed ?
d. How much heat (BTU) that must be removed to keep the final
temperature of the product solution calculated in part (c) at 77
o
F??
( )( ) ( )( )
( ) water mL 260
L
1000mL

kg 1
L
kg 0.2596 m
O H kg 0.2596 m ........
m 0.623
m 0 0.623 0.85
0.60
w
2 w
w
w
= |
.
|
\
|
|
|
.
|
\
|
=
=
+
+
=
( ) ( ) ( )
F , O H F , SO H % wt F , SO H % wt
o o o

60 60 85 77 60
2 4 2 4 2
i i i i i i
in
i i
out
i i
H m H m H m
H m H m Q
=
= =

JKG- FKKKSA
Page 8 - 26
From figure 8.5.1,
Alternatively, the heat transfer can estimated by the difference between the
enthalpy of the adiabatic solution and that of the solution at 77
o
F.
( )
( )
( )
Ibm
BTU
27.5 ~ H
Ibm
BTU
102.5 ~ H
Ibm
BTU
121 ~ H
F O,60 H
F ,60 SO 85wt%H
F ,77 SO 60wt%H
o
2
o
4 2
o
4 2
BTU 110.2 ~ H m H m Q
in
i i
out
i i
=

( ) ( )
BTU 110.7 - ~
H m H m H m H m Q
F ,77 SO 60wt%H i i F ,180 SO 60wt%H i i
in
i i
out
i i
o
4 2
o
4 2

= =

JKG- FKKKSA
Page 8 - 27
NH
3
-H
2
Fig. 8.5-2, p. 403, is a specific enthalpy of binary mixtures for
liquid-vapor equilibria in the ammonia + water system at 1 atm
pressure. It
has saturated liquid and vapor curves plus tie lines in the two-
phase region
can be used to solve energy balance problems, such as the flash
vaporization of ammonia + water mixtures
JKG- FKKKSA
Page 8 - 28
NH
3
-H
2
O Enthalpy-
Concentration Diagram
JKG- FKKKSA
Page 8 - 29
Enthalpy Concentration Charts
(Vapor Liquid Equilibrium)
An H x chart for ammonia-water
system at 1 atm is shown at several
temperatures.
A tie line is drawn on the enthalpy
concentration chart from x = 0.25 on
the liquid phase to the vapor-phase
curve at y = 0.95 at 100
o
F.
The tie line is to determine the
equilibrium composition and the specific
enthalpy of each phase at specified
temperature
JKG- FKKKSA
Page 8 - 30
Example 20 - prob. 8.98
An NH
3
-H
2
O mixture containing 60 wt % NH
3
is
brought to equilibrium in a closed container at 140
o
F.
The total mass of the mixture is 250 g. Use Fig. 8.5-
2 to determine the masses of ammonia and of water
in each phase of the system
Liquid phase , L, (~12.9 wt % NH
3
, 87.1 wt% H
2
O)
Vapour phase, V, (80 wt % NH
3
, 20 wt% H
2
O)
( )
lbm 0.164 L lbm 0.386 V
V L 0.55 : bal. Overall
0.8V 0.129L 0.55 0.60 : bal. Ammonia
lbm 0.55
1000g
lbm 2.2
x g 250 mass Total
= =
+ =
+ =
= =
35.1
64.9
140.4
9.65
Vapour
Liquid
H
2
O (gram) NH
3
(gram)
JKG- FKKKSA
Page 8 - 31
Working session 17 - Equilibrium Flash
Vaporization
A 30 wt% NH
3
solution at 100 psia is fed at a rate of 100 lb
m
/h to a
tank in which the pressure is 1 atm. The enthalpy of the feed
solution relative to the reference conditions is 100 Btu/lb
m
. The
vapor composition is to be 89 wt% NH
3
. Determine the temperature
of the stream leaving the tank, the mass fraction of NH
3
in the liquid
product, the flow rate of the liquid and vapor product streams, and
the rate at which heat must be transferred to the vaporizer.
JKG- FKKKSA
Page 8 - 32
From the figure
x
V
= 0.89 lb
m
NH
3
/lb
m
T = 120
o
F
x
L
= 0.185 lb
m
NH
3
/lb
m
H
V
= 728 Btu/lb
m
H
L
= 45 Btu/lb
m
100 lb
m
/h
0.3 lb
m
NH
3
/lb
m
H
F
= 100 Btu/lb
m
m
v
lb
m
/h
0.89 lb
m
NH
3
/lb
m
0.11 lb
m
H
2
O/lb
m
H
V
Btu/lb
m
m
L
lb
m
/h
x
L
lb
m
NH
3
/lb
m
(1-x
L
) lb
m
H
2
O/lb
m
H
L
Btu/lb
m
Working session 17
JKG- FKKKSA
Page 8 - 33
Working session 17
L V
F V
m
/h lb 100 x x
x x m
L
=
&
product liquid lb 84
185 . 0 89 . 0
3 . 0 89 . 0
/h lb 100
m m
=
|
.
|
\
|
=
L
m&
( ) product vapor lb 16 /h lb 84 - 100
m m
= =
V
m&
| | Btu/h 5400 Btu/h (100)(100) - (84)(45) (16)(728)
100

= + =
+ = =
F L L V V
H H m H m H Q & &
& &

15 Mixing and Solution

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SKF 2123 - Energy Balance

Instructor: Dr Azeman Mustafa

SKF 2123 - Energy Balance

(Hypothetical heating, cooling & isothermal mixing steps)

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