a CALORIMETRIC STUDIES OF

NEUTRALIZATION REACTIONS

JOHN G. MILLER, ARTHUR I. LOWELL,

and WALTER W. LUCASSE
University of Pennsylvania, Philadelphia,
Pennsylvania

TAERMOCAEMI~AL
studies of a wide variety of types Siuce AH, involves the severance of a bond in the weak
(4) are readily adapted for simplified undergraduate ex- acid, its sign would be expected to be opposite to that
perimentation. They may include determination of of AH2. In this event, the sum of AHl and AH2, that
the heat changes in strictly chemical processes, such as
the decomposition of hydrogen peroxide and numerous
other chemical reactions, and also the physisal aspects
HA -
is, the heat content change of the complete reaction
+ OH- H,O + A-
would be smaller in magnitude, as is found in most
of thermochemistry, such as heats of solution and dilu-
tion. Neutralization reactions, however, are m&t cases, than - 13.8kg.-cal.
frequently employed to exemplify the methods and Such a picture, however, fails to explain the ocour-
calculdtions of thermochemistry. The speed of such rence of values greater than -13.8 kg.-cal. and gives
reactions, the drill in preparing solutions of acids and an erroneously simple interpretation of the heat of
bases of definite concentration, and the importance of ionization. It must be emphasized that the solvent
the results in connection with the classroom work on the plays an important part in all acid-base reactions and an
theory of solutions have made these reactions almost the additional step may be introduced. Thus, for a weak
exclusive choice of nearly every laboratory text. acid and strong base, the steps are given more accurately
It is, perhaps, unfortunate that acid-base studies are as
uhally restricted to strong electrolytes. Use of weak
acids and bases and of polybasic acids not only requires
fuller understanding in the selection of indicators for the
H + +A-
HA-H++A-
+ (Z + y)H,O -- +
H+.zH20 +A- .yH1O
H + %HsO + OH- (z 1)H20
preparation of the solutions but also demands more
thought in the interpretation of the thermochemical
results. From his work with strong acids and bases,
the student concludes that these substauces are com-
and the total reaction is
HA +OH- + (Z + y)H.O -+ (Z 1)HsO +A- .yH?O
The first two steps, normally written as a single one,
taken together show the effect of the solvent. It is
pletely ionized and, in simplest form, writes the funda-
mental reaction:
H + + OH- - HnO; AH = -13.8 kg.-cal. (at 20°C.)
the sum of the heat content changes for these two steps
that is commonly considered the heat of ionization in
solution. This quantity includes, in addition to the
Because of the constancy of the value of AH Per mol of heat absorbed to break the bond in the acid, all of the
water formed, irrespective of the strong acid or base effects on the heat of ionization due to the medium in
used, he is unprepared to find such values of the heat which the acid is dissociated. A convenient way to
content change as -16.1 kg.-cal. for the reaction be- show this is to write the process in two steps, as above,
tween hydrogen fluoride and potassium hydroxide, stressing thus one of the major effects, that of solvation
-12.3 kg.-oal. for that between hydrogen chloride and of the ions. It is best, however, not to imply that this
ammonium hydroxide, and -11.9 kg.-cal. for that be- solvation involves a definite number of molecules of
tween formic acid and ammonium hydroxide. water nor that it is the only effect due to the solvent.
The additional factors which are involved with weak Since the solvation of the ions is an exothermic proc-
acids and bases may be emphasized by experimentation ess, the heat content change of the complete reaction is
and by consideration of the effects of the additional the algebraic sum of three two of which rep-
processes which take place in such cases. If, in ad&- resent heat evolved. The apparent h,eat content change
tion to the formation of water from its ions, the only of the major reaction, the formation of water, may be
reaction is the breakdown of the weak electrolyte, the increased or decreased depending upon the dominance
value of the over-all heat change will deviate from of the effect of solvation or of dissociation. Indeed,
-13.8 kg.-call. by an amount corresponding to the the role of the solvent explains why some neutraliza-
simple heat of ionization. Thus, the steps for the tion reactions, such as that of sulfuric acid with a strong
reaction of a weak acid with a strong base might be base, are more exothermic than the strong acid-base
written: reactions in which all of the reactant ions are already
HA-Ht+A-;
H + OH-
+ - AH,
H20; AH%
fully solvated, the strong electrolytes being completely
ionized when dissolved. The solvent effect is particu-
121
 122 JOURNAL OF CHEMICAL EDUCATION

lady well shown with polybasic acids. In allowing the plete reaction; 0.5 N tartaric acid was treated with
reaction to take place in steps, successive ionization equal volumes of 0.25 and 0.5 N base.
liberates further ions to become solvated with resultant SuIfamic Acid: This substance, NH2SO3H, was
thermal effects. chosen because it is a strong acid of unusual qualities,
Finally, the fundamental concepts are still more being a stable, nonhygroscopic solid. Because no values
clarified when studies of reactions of strong, weak, and of the specific heat and density are given in the literature
polybasic acids with strong bases are combined with the for 0.5 N sulfamic acid, 0.25 N sodium sulfamate, nor
parallel use of a weak base, such as ammonium hydrox- 0.25 N ammonium sulfamate, each measurement per-
ide, and with experiments on the heat of solution of mitted calculation of only one value of the heat of neu-
salts. For example, the heat of reaction of hydrochlo- tralization on the assumption that the product of the
ric acid with ammonium hydroxide and the heat of density and specific heat of each solution is equal to
solution of ammonium chloride are related. The fact unity. In two experiments, the values of AH obtained
that the solution of ammonium chloride in water is an for the sodium hydroxide reaction were -13.07 and
endothermic reaction indicates that the solvation of the -13.01 kg.-cal. in the temperature range from 27 to
ammonium ion is negligible and thus the heat of re- 30°C. No values are reported in the literature for
action of hydrochloric acid with ammonium hydroxide, comparison, but it is seen that the typical strong acid
being virtually due to only two opposing factors, is behavior is shown. With ammonium hydroxide two
understandably low. Although the hydroxyl ion is not values for. AH in the range from 26 to 2 9 T . were
commonly so written, it probably is solvated and this obtained, -11.44 and -11.43 kg.-cal., the difference
should be taken into account in certain cases. In the from the strong-base value being comparable with that
neutralization of ammonium hydroxide, however, the shown by other strong acids upon reaction with ammo-
heat of solvation of the hydroxyl ion is canceled out in nium hydroxide.
the over-all process, just as that of the hydrogen ion is Acetic Acid: With acetic acid and sodium hydroxide
in a weak acid-strong base reaction. the average value of AH a t 26'C. was -12.65 kg.-cal.
Experimental studies of the heat of reaction of the and a t 29.1°C. was -12.67 kg.-cal., which compare
following acids with, first, a strong base (sodium hy- favorably with the literature values and attest the re-
droxide) and, then, a weak base (ammonium hydroxide) liability of the apparatus and the method. The re-
have been found convenient and present a varied set of action with ammonium hydroxide, giving - 10.94 kg.-
effects: a strong acid (sulfamic), a weak acid (acetic), cal. at 26.2"C. and - 11.43 kg.-cal. at 29.0°C., indicates
a stronger weak acid (monochloroacetic), and two di- a high temperature effect due to change in the heat of
basic acids (oxalic and tartaric). In each case the heat iqnization and primarily to the low specific heat of the
effect is conveniently large at concentrations desirable salt solutions involved.
for work. All of the reactants are readily available and Monochloroacetic Acid: With monochloroacetic acid
reasonably soluble, and preparation and standardization and sodium hydroxide an average AH value of -13.73
of the solutions are facilitated by the fact that four of kg.-cal. was found at 24.6'C., which is about 4 per
the acids are stable solids. In laboratories in which cent lower than the value given in the literature for 18'
acetic acid of known concentration is available for other C. The relatively high value of the heat content change
experiments, conductance for example (3), this might can be attributed to the dual effect of solvation and
be used as a basis upon which to standardize sodium fairly high ionization. Using the same acid with am-
hydroxide and this in turn to prepare standard hydro- monium hydroxide, the energy of dissociation of the
chloric acid. Using these two, solutions of any acids weak base came into play and led to a vdue of - 12.2
and bases, strong or weak, can be prepared of desired kg.-cal. at 24.3'C.
concentration. It is instructive, however, to use sul- Oxalic Aeid: When the concentration of acid was
famic acid both as a representative strong acid in ther- such that only the first hydrogen was removed by the
mal study and as a primary basis for standardization addition of sodium hydroxide, the heat content change
U,Q was found to be -13.87 kg.-cal. (28.7T.), and when
I n obtaining the data given below, the method of both were removed, -14.03 kg.-cal. (25.2'C.). Using
procedure and calculation was the same as that de- ammonium hydroxide, the heat of dissocation of the
scribed in an earlier paper (4).' For the studies with base was such as to render the corresponding values of
monobasic acids, 0.5 N solutions of acid and base were AH, -12.01 kg.-cal. (27.8'C.) and -12.90 (25.1°C.).
used in all cases: For the dibasic acids, stepwise re- These values appear to agree with literature values.
action was achieved by treating 0.5 N base with an Tartaric Acid: In the work with tartaric acid the
equal volume (200 cc., as throughout) of 1.0 N oxalic concentration of the base rather than that of the acid
acid to cause half neutralization and 0.5 N acid for com- was altered to achieve partial and complete neutraliza-
tion. Parenthetically, it might be noted that in ther-
'The numerical data given in the earlier paper, except in
Figure 4, are in large calories and should have been designated mochemistry the term "neutralization" is not used with
as kg.-cal.; the equations for calculation, however, are in terms the same regard for hydrolysis as in titration and does
of small coalories. For consistenoy with Figure 4, the signs for not imply that the solutions are neutral a t the end
the heats of solution of sodium acetate should have been reversed,
that for the anhydrous being -3.86 kg.-cal. and for the tn- ~ o i u t . Sufficientdata were available in the case of the
hydrate 4.85 kg.-cal. (Continued on page 128)
 CALORIMETRIC STUDIES OF NEUTRALIZATION REACTIONS
(Continuedf ~ o mpage 1$2)

tartaric acid-sodium hydroxide iyuretns ro calculate the use of an approximate calculation in several cases.
-
thrrrnnl rllunee :it i)orl~the initial rind the final tcnmera- Finally, the high temperature coefficient of ionization of
tures. When the concentration of the sodium hy- weak electrolytes is reflected in large differences in the
droxide was such as to remove only the &st hydrogen, heat of reaction at different temperatures whenever such
the heat content change was -12.69 kg.-cal. a t 24.3OC. electrolytes are involved. Thus, the heat of dissocia-
and -12.67 kg.-cal. a t 25.g°C., indicating almost no tion of ammonium hydroxide, 1240, 790, and -470 kg.-
temperature coefficient over this range. With sodium cal. at 18', 25', and 51' C., respectively, is typical and
hydroxide of sufficient concentration for complete nen- wduld suggest sensitivity to temperature for any re-
'

tralization, however, the values at the lower (21.7"C.) action in which it enters. In the above experiments,
and higher (24.7OC.) temperatures were found to be however, the expected order of magnitude of the heat
- 11.21kg.-cal. and - 13.90 kg.-cal., respectively. The content change is shown in all cmes and from such
difference at the two temperatures is due largely to the studie's the average student receives a clearer insight
abnormally low value of the specific heat of solutions of into the nature of the heat of formation of water from
normal sodium tartrate (5). The values for its ions, the heat of ionization, and of solvation.
and com~letereaction of tartaric acid with ammonium
hydroxide were found to be -11.32 kg.-cal. (25.7'C.) LITERATURE CITED
and - 11.29 (24.7'C.), respectively.
Whenever temperature and other conditions made it ( 1 ) BOOTH,H. S., AND V. R.DAMERELL, "~uantitativeAnaly-
sis," McGraw-Hill Book Company, NewYork,l944, p. 181.
possible, comparison of the results of check experiments ( 2 ) B ~M. J., ~G. F. sMITH,
~ ~ L. F.
AND ~ A,,Dn IETH,
, Eng.
of the above studies showed excellent agreement; Chem., Anal. Ed., 10, 690 (1938).
however. several factors combine to make difficult anv (3) ~. MILLER,J. G.. AND W. W. LUCASSE, J. CHEM.EDUC.. . 22..
rigid evkuation of the data. Where comparable work 565 (i945).
on Q . ,+
~,D.
", B., J. G. MILLER,AND W. W. LUCASSE,
appears in the literature, it is usually of an early date (4) PAPISON,
'U, O'J (
'
3"
)
.
ibid.,
&h probable inaccuracy of experim+ation. Further- (5) RICRAEDS, T. w.,AND F. T. GUCKER, J . Am. Chem. SOC., 47,
more, lack of specific heat and denwty values force the 1889 (1925).