883

Changes in Concentration of Solutions of Volatile Solutes

K. W. Allen
Department of Chemistry, The City University, St. John Street, London, E C l V 4PB

Keywords : Volatile solutes ; titrimetric analysis

When successive aliquots are withdrawn from a solution, whether by pipette for conventional analysis or by other means, the assumption is tacitly made that the concentration of the solution remains constant. Although this may be generally true for the usual type of involatile 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 precisely controlled, the solvent will always be volatile and this will involve some alteration in cornposition. These effects can be considered and the results analysed provided that a suitably consistent regime 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 Physics1 (they are not quoted in later editions). Consider a closed vessel of total volume V containing the solution and with some free

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space above the liquid, with the temperature of the surroundings T K and the atmospheric pressure P both constant. Then initially the vessel contains: (i) a volume of liquid Vlothat has a composition CAO,C moll-1 of the two com, ponents A and B, respectively; and (ii) a volume of vapour - vlo) has a composition kcAo, iCB0 mol l-l, where k that 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 the partial pressures p o, pBo of the two components A and B, respectively, which will have volatilised after the vessel was closed. These partial pressures are given by

(v

assuming that the ideal gas laws apply and remembering that kC = n/V and also by

p*o = P

A (cAO

cBO)

assuming that Raoult's law applies, where PA and PBare the vapour pressures of the pure materials A and B, respectively, at the temperature T. We therefore have
or _= pAO = RT(RCAO
PAC,, cAO

+ +
PBO
p5c50 cBO

jcBO)

+ +

Now a sample is withdrawn according to the following scheme:

Stage 1: The vessel is opened to the atmosphere, when there is an immediate adiabatic expansion of the vapour contents. 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 temperature T . This cycle of three stages can be repeated in order to remove successive aliquots as many times as may be necessary. By consideration of the concentration changes through the stages of the scheme, the relevant relationships throughout the whole process can be established. Stage 1: Here there is an adiabatic expansion from (P + 8) to P , so

where CAIis the composition that the liquid would have had if equilibrium had been established at this point arid y is ratio of specific heats of an ideal gas.

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where and also Similarly for B. Also,

T,

AY-l

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 an equal 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 artificial to consider the atmosphere to contain any concentration of the solute it will probably contain some solvent, certainly if the solvent is water. At the end of this stage, the total contents may be considered to be made up of three parts: CBo at temperature T ; (i) liquid of volume ( V , - I ) and of composition CAO, (ii) vapour of volume (V - V , - v ) and of composition kCA1, jCBl a t partial pressures and a t temperature T,; v ) and of composition r, s a t partial pressures PA, = RTr, (111) air of volume (I PB, = RTs, and a t temperature T .

Stage 3: Now the whole system is brought back to equilibrium to temperature T,with final liquid concentrations c A 3 and c B 3 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 a t the end of stage 2 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 in terms of the various volumes involved, standard physico-chemical properties of the components 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 a t 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 the stopper. When a 25-ml pipette is inserted in order to remove samples it will displace about

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5 m l of vapour. Then, if 25-ml samples are removed following the regime indicated, the calculation is as follows. As k for bromine is not readily available, it can be calculated from the solubility (31.6 g per 1000 g of water), the vapour pressure (214 mm) and the relative molecular mass of bromine (160). With these units, R = 62.4. Thus,

CA = 31.6/160moll-l
kC,
Hence k =
214 160 - 0.05827 298R x 31.6= P/RT = 214/298R

Now, for the main calculation V = 265m1, V l o = 250m1, Z = 25m1, ZI = 5 ml, PBr2 = 214mm, PH2,, 23.7mm, T = 298K, P = 760mm and r = 0. Taking bromine as = component A and water as component B, we have C , , = 0.1 moll-1 and C,, = 55.56 moll-l. Then,

6=

(214 x 0.1)

(23.7 x 55.56) 55.56

= 24.09 mm

and
= (760

+ 24.09

>""35

= 0.9772

The main relationship gives 0.1[(250 - 25) and therefore

+ 0.9772

0.05827 (265 - 250 - 5)] = CA3[(250 25) -

+ 0.05827 (265 - 250 + 25)]

Cd3= 0.0992

Number of samples withdrawn

Fig. 1. Change in concentration of liquid as samples are withdrawn according to regime described. The positions of the points have been determined experimentally and the curve has been calculated.

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Thus, after one operation the concentration of the solution has been reduced by 0 8 simply .% as a result of the act of sampling. This calculation can be repeated for a series of successive samplings. The results of these successive calculations and of a series of experimental determinations are shown in Fig. 1. Acknowledgement is made of the assistance of the late Dr. Paul White, for without his help and encouragement the work would never have been completed.

Reference
1. Handbook of Chemistry and Physics, Twenty-first Edition, Chemical Rubber Publishing Co., Cleveland, 1936. Received March lst, 1978 Accepted March loth, 1978