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14
H2SO4-balance
1,in m
2,in
m
1,in
2m
1,in x H SO ,2,in m
2,in x H SO ,out m
out
x H2SO4 ,1,in m
2
4
2
4
1,in 0.9 m
1,in x H SO ,out 2 m
1,in
0.1 m
2
H
1,in H 2,in H out
H
1,in m1,in H 2,in m 2,in H out m out
H
1,in H 2,in
out
2
H
1,in 40
kg
kJ
H
2,in 0
kg
kJ
Thus, Hout 20 kg
The final temperature can be found by looking at the curve going through
the point of 50 wt.-% sulphuric acid and a specific enthalpy of 20 kJ/kg.
This results in a temperature of ca. 100 oC (coming rather close to the vaporliquid region boiling danger!)
kJ
H
1,in 40
kg
kJ
H
2,in 325
kg
kJ
Explain why the adiabatic mixing temperature is greater than that of either
of the initial solutions in one of the cases and intermediate between those
of the initial solution in the other case.
The adiabatic mixing temperature is a result of the heat of mixing. The heat
of mixing can be seen as the difference in the A-B interaction and the A-A
and B-B interactions of the pure fluid. Hence, mixing relatively pure
substances (as in part a) will result in more A-B interactions than A-A and AB interactions. This will lead to an increase in temperature, if A-B
interactions are energetically favored over either A-A and B-B interactions.
In part (b) the relative pure mixture is mixed with a already dilute mixture.
Furthermore, we can consider the shape of the enthalpy curves as a function
of the weight percentage of sulphuric acid. It shows a minimum at ca. 60
wt.-% sulphuric acid (this corresponds to a molar water to sulphuric acid
ratio of ca. 3.8). The resulting enthalpy upon mixing of two mixtures
containing less than 60 wt.-% sulphuric acid will be approximately on the
curve, whereas mixing solutions on both sides of the minimum will result in a
much higher enthalpy than predicted by the isotherm(s).
Question 8.15
The molar integral heat of solution is defined as the change in enthalpy that
results when 1 mole of solute is isothermally mixed with N 2 moles of solvent.
The molar integral heat of solution is easily measured in an isothermal
calorimeter by monitoring the heat evolved or adsorbed on successive
addition of solvent to a given amount of solute.
a. Calculate the heat evolved when 100 g of pure sulphuric acid is added
isothermally to 100g of water.
The molar mass of H2SO4 98 g/mole
The molar mass of H2O 18 g/mole
Thus, we are mixing 1.02 mole of sulphuric acid with 5.55 mole of water (or a
molar water to sulphuric acid ratio of 5.44). The integral heat of solution for
the addition of 5.44 mole of water to 1 mole of sulphuric acid is given as
58.370 kJ. Hence the heat evolved is 1.02*58.370 = 59,561 kJ
b. Calculate the heat evolved when the solution prepared in part a) is
diluted with an additional 100 g of water
The process can be thought to occur via two sub-processes:
1 Splitting the solution in 1.02 mole sulphuric acid and 5.55 mole of water:
heat adsorbed = 59.561 kJ
2 Mixing 1.02 mole with 11.11 mole of water (molar ratio water to sulphuric
acid 10.89). By interpolation the integral heat of solution of 1 mole of
sulphuric acid with 10.89 mole of water is 65.37 kJ. Thus, the heat
evolved is 1.02*65.37 kJ = 66.703 kJ
For the overall process the heat evolved is thus7.142 kJ
H s H1 H1 N 2 H 2 H 2
(for a solution containing 1 mole of sulphuric acid and N 2 mole of water; for a
solution containing N1 mole of sulphuric acid and N2 mole of water, i.e. the
molar ratio of water to sulphuric acid to water in the solution is N 2/N:
N
Hs H1 H1 2 H 2 H2 )
N1
Hs
N2
N
1
H1
N2
N
1
H1
N2
N
1
H2 H2
N2
N1
N2
N
1
N2 H2
N H2
2
N1 N2 N1 N2
N
N
1
1
The partial molar property of the pure substances H1 and H2 are independent
of N1 and N2 (and thus independent of their ratio as well)
H1
H2
0
0
N2
N2
N1
N1
N
2
N1 N 2 H2
Hs
H1
H 2 H2
N2
N2
N2 N1 N2
N
N
N
N
1
1
1
1
N2
N
1
The differential
H s
N
2
N1
N
2
N1
N H 2
H1
H2 H2 2
N
N1 N 2
2
N
N1
1
N1
N1
N H 2
H1
2
0
N 2 N1 N 2
N1
N1
H s
H2 H 2
N2
N1
This thus yields the 2nd equation for our variables. Solving for the variables:
H
H
H2
Hs
N2
N1
H1 H s
N2 Hs
N1 N 2
N1
N2
N1
kJ
Thus, H 2 H 2 4 mol H O
2
kJ
It can thus be deduced that the interaction of sulphuric acid in the solution
is quite different from the interaction in pure sulphuric acid and the high
heat of mixing is mainly due to sulphuric acid.
Question 8.26
Mattingley and Fernby (1975) have reported that the enthalpies of
triethylamine-benzene solutions at 298.15K are given by
Where xB is the mole fraction of benzene and Hmix, HB and HEA are the molar
enthalpies of the mixture, pure benzene and pure triethylamine.
a. Develop expressions for HB HB and HEA HEA
The change in the molar enthalpy upon mixing is defined as
H
H
mix H
x
1 x B
HB
HEA
HB HB B x B
x B B HEA HEA
1 x B
1 x B EA
x B
x B
x B
x B
x B
x B
x B
The pure component molar enthalpy Hi with respect to the mol fraction is
independent of the mole fraction of the mixture.
mix H
x
1 x B
HB
HEA
HB HB B x B
HEA HEA
1 x B
x B
x B
x B
x B
x B
HB
HEA
NEA
0
NB
NB
xB
HB
HEA
x EA
0
NB
NB
xB
HB
HEA
1 x B
0
NB
NB
mix H
x
1 x B
HB HB B HEA HEA
x B
x B
x B
mix H
HB HB HEA HEA
x B
H
H
mix H
x B HB HB x B HEA HEA
x B
xB
EA
HEA mix H x B
mix H
x B
HB mix H 1 x B
EA
HEA mix H x B
mix H
x B
mix H
x B
mix H
1 x B 1418 482.4 1 2 x B 187.4 1 2 x B 3
x B
x B 1 x B 964.8 1124 .4 1 2 x B
EA
HEA mix H x B
mix H
x B
x B 2 1 x B 964.8 1124 .4 1 2 x B 2
EA
x B 2 1 x B 964.8 1124 .4 1 2 x B 2
x B 1 x B 964.8 1124 .4 1 2 x B
2
HB 475.1
J
mol
EA
HEA 233.9
J
mol
Hmix x B HB 1 x B HEA