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883
Changes in Concentration
of
Solutions of VolatileSolutes
K.
W.
Allen
Department
of
Chemistry, The City University, St. John Street, London, EClV
4PB
Keywords
:
Volatile
solutes
;
itrimetric analysis
When successive aliquots are withdrawn from a solution, whether by pipette for conventionalanalysis or by other means, the assumption is tacitly made that the concentration of thesolution remains constant. Although this may be generally true for the usual typeofinvolatile solutes in aqueous solution,
it
is not true if the solute
is
appreciably volatile.Indeed, it is probably never strictly true because, unless the conditions are very preciselycontrolled, the solvent will always be volatile and this will involve some alteration incorn posit on.These effects can be considered and the results analysed provided that
a
suitably consistentregime is adopted. This paper defines such a regime and then considers the consequences.All data have been taken from an early edition
of
the “Handbook of Chemistry and Physics”1(they are not quoted in later editions).Consider a closed vessel
of
total volume
V
containing the solution and with
some
free
 
884
SHORT
PAPERS
Analyst,
VoE.
103
space above the liquid, with the temperature of the surroundings
T
K
and the atmosphericpressure
P
both constant. Then initially the vessel contains:
(i)
a volume of liquid
Vlo
hat has a composition
CAO,
C,,
moll-1 of the two com-ponents
A
and
B,
respectively; and(ii) a volume of vapour
(v
-
vlo)
hat has
a
composition
kcAo, CB0
mol l-l, where
k
and
j
are the reciprocals
of
the respective Henry's law constants.The pressure inside the vessel will be
(P
+
S),
higher than the suroundings because of thepartial pressures
p
o,
pBo
of
the two components
A
and
B,
respectively, which will havevolatilised after the vessel was closed.These partial pressures are given byassuming that the ideal gas laws apply and remembering that
kC
=
n/V
and also by
p*o
=
PA
cAO
?
BO)
assuming that Raoult's law applies, where
PA
and
PB
are the vapour pressures of the purematerials
A
and
B,
respectively, at the temperature
T.
We therefore have
=
pAO
+
PBO
=
RT(RCAO
+
cBO)
or
-
PAC,,
+
p5c50
cAO
+
cBO
Now a sample is withdrawn according to the following scheme:
Stage
1:
of the vapour contents.The vessel is opened to the atmosphere
,
when there is an immediate adiabatic expansion
Stage
2:
Quickly, so that there is effectively no interchange between the solution and the vapour,
a
sample of both liquid and vapour is removed and is replaced with an equal volume of air(which may contain some of components
A
and/or
B).
Then the vessel is closed.
Stage
3:
The remaining contents of the vessel are allowed to re-attain equilibrium
at
the tempera-ture
T.
This cycle of three stages can be repeated in order to remove successive aliquots as manytimes as may be necessary. By consideration of the concentration changes through thestages
of
the scheme, the relevant relationships throughout the whole process can beestablished.
Stage
1:
Here there is an adiabatic expansion from
(P
+
8)
to
P,
so
where
CAI
s the composition that the liquid would have had if equilibrium had been estab-lished at this point arid
y
is ratio of specific heats of an ideal gas.
 
A
%gust
1978
SHORT
PAPERS
885
whereand alsoSimilarly for
B.
Also,
T,
=
AY-l
T
as a result of the adiabatic cooling of the vapour.
Stage
2:Here a volume of vapour and a volume
of
liquid
I
are removed and replaced with anequal volume of air containing concentrations
Y
and
s
of
A
and
B,
respectively. Of course,
r
or
s
may either or both be negligibly small, with subsequent simplification.Note that the volume of vapour removed may simply be due to displacement as
a
result
of
inserting the pipette or sampling device, and that whereas
it
may be somewhat artificialto consider the atmosphere to contain any concentration
of
the solute
it
will probably containsome solvent, certainly
if
the solvent is water.
At
the end
of
this stage, the total contentsmay be considered to be made up of three parts:
(i)
(ii)
(111)
liquid
of
volume
(V,
-
)
and of composition
CAO,
CBo
at temperature
T;
vapour
of
volume
(V
-
V,
-
)
andofcomposition
kCA1,
jCBl
at partial pressuresand at temperature
T,;
air of volume
(I
+
v)
and of composition
r,
s
at partial pressures
PA,
=
RTr,
PB,
=
RTs,
and at temperature
T.
Stage
3:
Now the whole system is brought back
to
equilibrium to temperature
T,
ith
final liquidconcentrations
cA3
and
cB3
and corresponding vapour concentrations of
KC,,
and
jC,,
and a final pressure of
P
+
6.
The total amounts of each component inside the vessel can be equated at the end of stage2 and at the end of stage
3.
For component
A:
and similarly for component
R:
This has now given relationships between successive concentrations of each component interms of the various volumes involved, standard physico-chemical properties of the com-ponents and the conditions of the surroundings.As a typical example, consider a
0.1
M
solution
of
bromine in water in an environment
of
pure dry air at
760
mm pressure and
25
"C.
If
this is in
a
conventional 250-ml calibrated
flask,
typically there will be a free space
of
15
ml above the calibration mark and below thestopper. When
a
25-ml pipette is inserted in order to remove samples
it
will displace about

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