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16 THERMOMETRIC TITRIMETRY [Proc. SOC.Analyt. Chem.

Thermometric Titrimetry
The following are summaries of papers presented at the Joint Meeting of the Midlands
Section of the Society and the Birmingham and Midlands Section of the Royal Institute of
Published on 01 January 1966. Downloaded by University of Illinois at Chicago on 28/10/2014 21:14:01.

Chemistry held on September 15th, 1965, and reported in the October issue of Proceedings
(p. 147).

Introduction to Thermometric Titrimetry

BY L. S. BARK
(Royal College of Advanced Technology, Salford, Lancashive)

MR. BARKstated that as a thermometric titration utilised the enthalpy change of a reaction
to locate the end-point of the reaction, it could be defined as a titration in an adiabatic system,
in which the temperature was plotted against the volume of the titrant used.
As most reactions showed detectable heat changes, thermometric methods could be used
for various types of reactions. Factors, such as adverse colour changes and turbidity (arising
from the original sample, or caused by precipitation of materials from solution), which
affected photometric titrations, and which might have an adverse effect on electrode systems
in electrometric methods, had no significant effect on thermometric methods.
The apparatus used for thermometric titrations was essentially a burette in conjunction
with a sensitive device for measuring the temperature change of the titrand system. The
earliest type of apparatus used had comprised a thermostatted burette that delivered the
titrant into a titrand contained in a Dewar flask. The temperature change had been measured
with a Beckmann thermometer or one of similar sensitivity. Although the time required for
a simple titration with this type of system had been approximately 45 to 60 minutes, deter-
minations such as those of calcium with oxalate, the calcium-to-magnesium ratio in dolomite
and investigation of basic-salt formation of beryllium, cobalt and nickel compounds had
been made.
The first major advance had been made in 1953 by replacing the thermometer with a
thermistor bridge capable of recording temperature change, and replacing the simple burette
with a constant-flow burette. The introduction of an automatic-piston burette in 1957 had
completed the system, which was now considered to be the basic apparatus for thermometric
titrations.
Further development had depended on the particular rate of delivery of titrant. Fast
delivery had been advocated by some workers, who used the rapid change in temperature
and consequent large change in bridge current to enable first and second derivative curves
to be drawn, thus indicating, more clearly, the points at which relatively large heats of
reaction occurred. The heat losses or gains (due to ambient temperature changes) of titra-
tions that could be made in 10 to 20 seconds were not large enough to interfere with end-point
detection and had therefore obviated the need for a thermostating of the titrand in a Dewar
flask. It had also been possible to automate the burette, so that the titration became a
“dead-stop” titration and the titre was presented digitally or on paper. This method was
claimed to achieve a greater accuracy than that obtained by using the normal type of recorder
and chart paper and hence calculating the volume of the titrant used by measuring the length
of trace on the paper.
Other workers who had used a slow delivery of titrant claimed to be able to determine
multiple equivalence-point titrations with greater accuracy.
Among the various determinations that had been made were acid - base, redox, pre-
cipitation, complexometric and simple non-aqueous titrations.
Titrations in organic solvents were readily accomplished by this method, the low specific
heat of the materials used allowed small energy changes to give relatively large temperature
changes.
It was suggested that further advances would be made by improving the metering of the
flow and the delivery of the titrant and in electronic amplification of the signal that was
received from the thermistor.
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February, 19661 THERMOMETRIC TITRIMETRY 17

Thermodynamic Background and Possible Application to Analytical Probleins

BY H. J. V. TYRRELL
(Chelsea College of Science and Technology, Manresa Road, London, S . W.3)
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PROFESSOR TYRRELL said that most reactions involved an evolution or absorption of heat,
the amount of heat evolved being a function of the molar enthalpy change in the reaction,
and of the extent to which the reaction had taken place. When the reaction was complete,
further addition of reagent normally gave rise to a much smaller heat change that arose from
the dilution of the reagent. Therefore, if the heat evolved per unit addition of reagent was
measured, there would, in general, be a detectable change in this amount when the reaction
was complete, i.e., at the end-point. An enthalfiimetric titration then became a possibility. As
heat evolution could not be measured directly, but only temperature changes, the name
thermometric titration was to be preferred. The ease of detection of the end-point depended
upon the size of the enthalpy change in the reaction, in contrast with normal titrimetric
procedures where the sharpness of the end-point depended upon the magnitude of one or
more equilibrium constants, i.e., upon standard free-energy changes. A large enthalpy
change might be associated with an unfavourable free-energy change, and, for this reason,
reactions unsuitable for normal titrimetric procedures might give sharp end-points in a
thermometric titration. A striking example was the ease with which weak acids such as
boric acid and the ammonium ion might be determined with a thermometric end-point, by
titration with alkali. The enthalpy change could be either positive or negative as long as it
was sufficiently large. Recent advances in instrumentation had made it possible to carry
out such titrations easily and quickly.
The method had been widely applied to aqueous and non-aqueous solutions, and even
to certain fused-salt systems. The chief disadvantage might be lack of selectivity, associated
with the fact that almost all reactions showed a sizeable value of AH, but sometimes kinetic
factors could intervene in a favourable manner. For example, calcium could be determined
in the presence of magnesium with oxalate; this was because the precipitation of magnesium
oxalate was too slow to occur in the short time required for the experiment to be completed.
Thermometric titrations could also be used in principle to measure enthalpy and free-energy
changes in reactions; the principal problem was the improvement of the experimental tech-
niques so as to achieve the highest possible accuracy in measurement of the temperature
changes.

An Apparatus for Recording Thermometric Titration Curves

BY W. S. SEBBORN
(Research Laboratory, Kodak Ltd., Wealdstone, Harrow)

MR. SEBBORN described the apparatus constructed and used in the Kodak Research Labora-
tory which was based on work described by Jordan and Alleman and by Zenchelsky and
Sagatto, and which now contained some important modifications that enabled it to be con-
siderably simplified. By using a specially designed high-speed mixer, it was possible to
add the titrant at a rate of up to 10 ml per minute, so allowing a titration to be completed
in 20 seconds or less. This not only allowed the derivative of the temperature-time curve
to be used, so giving sharper end-point discrimination, but also rendered less significant
those heat losses or gains due to small changes in ambient temperature, and eliminated the
need to carry out titrations in Dewar vessels. Titrations were carried out in polythene
beakers of about 50 ml capacity.
The stirrer used was a circular paddle made from Perspex lying in a horizontal plane and
drilled with oblique holes in a random fashion. This paddle was supported by a central
vertical spindle formed from an F23 (Standard Telephones & Cables Ltd.) thermistor and was
attached by this to a vibration generator operating at mains frequency. By this arrange-
ment the paddle could be vibrated in a vertical plane with an amplitude of about inch.
The diameter of the paddle was chosen so that there was minimal clearance between it andthe
wall of the polythene beaker used as the titration vessel.
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18 THERMOMETRIC TITRIMETRY [Proc. SOC.Analyt. Chew.

The thermistor used, type F23, was in the form of a small glass-covered bead a t the
end of a thin rod. It was possible to use this to support the vibrating disc, and consequently
the relative position of the thermistor bead and the stirrer remained constant, thus eliminating
a possible source of variation.
At the time when work was carried out, a suitable burette was not commercially available
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and a syringe burette was constructed with a standard 5-ml Chance glass syringe giving a
delivery rate of 7 ml per minute.
Sensitivity of measurement was of the order of 0-001°C. Temperature changes and times
were followed on a recording millivoltmeter, similar to the practice of earlier workers, but it
was found more convenient to replace the normal bridge circuit with one giving constant sensi-
tivity over a temperature range of 15" to 30" C.
Because titration times were from 10 to 20 seconds duration, it became necessary to use
greater chart speeds than those employed by earlier workers in order to obtain the necessary
precision of measurement of time, and hence volume of titrant used. Speeds used were
about 30 inches per minute. This gave 10 inches of record per titration allowing k0.5 per
cent. accuracy in measurement of titre.
For routine titrations, involving a single end-point, the recording titrator was more
conveniently replaced by a digital read-out burette. The recording titrator was, however,
eminently suited for investigative work and for titrations involving multiple end-points.
Some typical reactions that had been studied were illustrated. These included titrations
with 0.1 N hydrochloric acid, showing (a) multiple end-points obtained in titration of photo-
graphic developer containing alkali carbonate and sulphite and (b) results of titration of silver
nitrate by hydrochloric acid, oxidation - reduction reactions with sulphate - cerate, iodine
and permanganate; and multiple cation titrations with EDTA. The use of interposition of
an endothermally reactive cation to sharpen the end-point of an exothermal reaction or to
improve separation of successive exothermal end-points was illustrated.
The advantages and wide applicability of thermometric titration were mentioned; most
determinations normally performed gravimetrically could be carried out volumetrically by
thermometric means. One thermistor took the place of various indicators or electrode
systems used in other techniques and maintenance was simple. At this stage of instrumenta-
tion however, it was not possible to work with such low concentrations as were possible with
potent iomet ric techniques.

Development of an Automatic Titrator with Digital Readaut

BY P. T. PRIESTLEY
AND M. SMITH
(Research Laboratory, Kodak Ltd., Wealdstone, Harrow)

MR. PRIESTLEY said that the recorded curve obtained in a thermometric titration showed
a temperature ordinate and a titre abscissa in millilitres that was equivalent to the distance
measured along the length of the chart. The straight-line portions of the curve were normally
extrapolated to give the initial and end-points of the titration, and the titre was given by the
value of the distance between the points of intersection. This method of evaluating the titre
was not satisfactory for routine operation, as it was tedious and introduced sources of error.
If the intial and end-points could be detected automatically, then the burette delivery could
be controlled so allowing measurement of the volume of titrant used in the titration. Alterna-
tively, with constant rate of delivery, the time interval between the points could be auto-
matically measured to give an evaluation of the titre.
Zenchelsky and Segatto, working in New Jersey during 1956, showed in a subsequent
paper how the first and second derivatives of the temperature - time plot could be used to
obtain sharper discrimination of the initial and end-points of the thermometric titration.
They proposed an upper limit in titrant-addition rate of 2 ml minute-l with 50 ml of titrand,
and in practice obtained rates of temperature change around 0.2"C minute-1, giving rise to an
output of 1 mV minute-1 from their thermistor-bridge circuit. This small signal was amplified
by using a servo-potentiometer system with a gain of lo5, and the amplified voltage was
differentiated by two resistance - capacitance networks, each having a time constant of 0.5
second. The titre was evaluated by measuring the distance between the two resulting peaks,
corresponding to the initial and end-points of the titration.
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February, 19661 THERMOMETRIC TITRIMETRY 19

Mr. Priestley said that Zenchelsky and Segatto's apparatus, together with his own method
of vibration stirring, had led him to believe that higher rates of titrant addition were possible,
thereby giving higher rates of change of temperature with time, and allowing relatively simple
electronic circuits to be used in the construction of an automatic titrator. A prototype was
constructed, which used a syringe burette with a constant rate of 7 ml minute-1, and which
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gave a typical output of about 50 mV minute-l, substantially larger than that obtained by
Zenchelsky. The signal from the thermistor was filtered and differentiated by a resistance -
capacitance network with a time constant of 50 milliseconds. The resulting square wave
was amplified by a transistorised amplifier to give a useful signal whose time period was the
required time or titre of the titration. The end-point detector comprised a transistorised
relay circuit that could detect sudden changes in its input voltage. The relay therefore
changed state as soon as the thermistor in the titrand detected a change of temperature, due
to the start of the titration, and it reverted to its original state when the temperature stopped
changing at the end-point.
The burette, which incorporated an electro-magnetic counter, was driven by a syn-
chronous motor and micrometer-screw mechanism that imparted linear motion to the piston
of a glass syringe. The latter was fitted with a pair of non-return valves arranged so that
fresh titrant was introduced into the syringe from a reservoir when the piston was withdrawn,
whilst in the other direction, titrant was dispensed through a delivery arm into the vessel
containing 25 ml of titrand. During a titration, the timer was set to count automatically
when the rate of temperature change exceeded 0.5" C minute-l. At the end-point the timing
counter stopped, no further titrant was dispensed and the burette automatically refilled. The
50 cycles second-1 mains frequency was used as a timing standard, and titres were shown t o
a precision of 0.02 second, in a useful titre range of, say, 5 to 20 seconds (0.5 to 2-0ml of
titrant).
The titrator has been used with titrations involving neutralisation, chelation, precipita-
tion and redox reactions. In general the 2-sigma (2 standard deviations) reproducibility
was about 1 per cent.

Thermometric Titrations of Some Precipitation Reactions

BY R. J. N. HARRIES
(Neath Technical College, Neath, Glamorgan)

MR. HARRIESdescribed an apparatus that was suitable for carrying out thermometric titra-
tions, comprising a 600-ml silvered Dewar flask as reaction vessel and a thermopile for tempera-
ture measurement. The thermopile was made of 30-s.w.~.copper wire, and cotton-covered
24-s.w.~.Eureka resistance wire, each junction being soldered and contained in a thin-glass
tube. Some mercury was placed a t the bottom of each glass tube in order to immerse the
junction and facilitate heat transfer. Twelve cold junctions and twelve hot junctions were
constructed. Each wire of the thermopile was about 50 cm long, and it was found to produce
0.0006 volt "C-l.
A glass stirrer, operating at about 300 r.p.m., was used to stir the reaction mixture. The
stirrer motor was not synchronous.
The burette was constructed from a uniform graduated glass capillary tube and delivered
0.10 ml of titrant in 15 seconds. A thin capillary tube was used to introduce the titrant into
the solution in the reaction vessel. It was made to dip just below the surface of the reacting
liquid. The relative positions of thermopile, stirrer and burette tip did not appear to be
critical .
The voltage from the thermopile was balanced on a Tinsley 3387B potentiometer with a
2-volt accumulator fitted with a voltage dropper as a storage cell. A Pye Scalamp galvano-
meter was used as the null-point detector, its graduated scale was removed and it was adapted
for use with a wall scale 70 cm away.
Mr. Harries outlined the procedure, in which a measured volume of the solution to be
analysed was placed in the Dewar vessel, and if necessary diluted, so that a reasonable galvano-
meter deflection was obtained on introducing 0.1 ml of titrant. The minimum volume that
could be used was 25 ml, or the thermopile would not be in contact with the solution. The
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20 THERMOMETRIC TITRIMETRY [Proc. SOC.Analyt. Chem.

stirrer was switched on and when thermal equilibrium was reached the burette tip was intro-
duced. The titrant temperature and laboratory temperature were not controlled. After
0.1 ml of titrant had been delivered into the reaction vessel the potentiometer reading was
taken for a t least five readings after the end-point. A graph of potentiometer reading
against volume of titrant was drawn, from which the end-point could be deduced.
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Silver nitrate titrations.-Satisfactory results were obtained with chloride, bromide,

iodide, ferricyanide, t hiocyanat e, oxalate, nitroprusside and chromate . With potassium
dichromate the formation of silver chromate was indicated; this was verified by analysis of
the precipitate (Ephraim, Inorganic Chemistry, 5th English Edition, Gurney and Jackson).
Potassium cyanide showed two arrest points corresponding to AgCN and Ag(CN),-.
With potassium ferrocyanide the formation of the heterometallic supercomplex
K(Fe(CN),Ag3) was shown by an intermediate arrest point, the final compound being
Ag(Fe(CN)6Ag3)*
Attempts to analyse orthophosphate, pyrophosphate, acetate, and cobaltinitrite failed
because of their small heats of reaction.
An attempt was made to analyse mixtures of chloride, bromide and iodide but this was
only partially successful becaus e co-precipitatio n occurred. Co-precipitation was found to
be least with iodide - bromide mixtures and most with bromide - chloride mixtures. It was
also found that co-precipitation was least when the halides were present in equimolecular
proportions. Iodide - bromide analysis was accurate to 1 per cent. when the ratio of I- to
Br- was 1 to 1, but could fall to as much as 10 per cent. if the ratio of I- to Br- was 4 to 1
or 1 to 4. Chloride - bromide analysis was more strongly affected by co-precipitation, the
ratio of chloride found to chloride added being as high as 1.385 when the ratio of Br- to C1-
was 4 to 1.’ (Kolthoff and Stenger, Volumetric Analysis, Volume I, 2nd revised Edition,
Interscience Publishers Inc. and Clarke, J. Chem. SOC.,1926, 768). It was found that the
addition of neutral electrolyte to decrease co-precipitation was unsuccessful. In all mixed-
halide titrations the total halide was found with an accuracy of less than 1 per cent.
Mercwous nitrate titrations.-Chloride, bromide, oxalate, cobalticyanide and nitro-
prusside, gave satisfactory results. Thiocyanate and iodide titrations failed because of dis-
proportionation of the mercurous compounds initially formed.
With potassium ferrocyanide an intermediate arrest point indicated the formation of a
heterometallic supercomplex I(,(Fe(CN),Hg,) that could not be isolated because of its de-
composition into products varying in colour from pale green to dark blue. The final com-
pound was Hg,(Fe(CN),Hg2),which was stable and was isolated and analysed.
With potassium permanganate, no stoicheiometry was found.

Acetone as Solvent in the Enthalpimetric Titration of Acidic Substances

BY G. A. VAUGHAN
(Coal T a v Reseavch Association, Gomevsal, Leeds)

MR. VAUGHAN said that the enthalpimetric titration of acidity with a non-aqueous alkali
often showed only a light change in slope at the end-point, but it had been found that if
acetone was used as the solvent for the acid, it acted as an “indicator.” A rapid rise in
temperature occurred at the neutralisation point, due to the formation of diacetone alcohol
from the reaction of the acetone with the excess alkali.
In order to make use of this “indicator” action it was necessary that the acetone was
dry and as free from carbon dioxide as possible, the non-aqueous titrant was concentrated
and added continuously with stirring and, if the sample had been dissolved in another solvent,
at least three times its volume of acetone had to be used. The method was applicable to a
wide range of acidic substances, including 2,6-disubstituted phenols, keto-enols and imides,
and could also be used to determine traces of acidity.
The complete paper has been published in The Analyst, 1965, 90, 594.