EXPERIMENT 14

Heat of Solution.
Calorimetric Method.

REFERENCES:

Physical Chemistry, Daniels and Alberty, L975 Chapter I

Physical Chemistry , Eggers, et aL. , L964 Chapter 9

Pundamentals of Physical Chemistry, Crockford

and Knight, 1964 Chapter 5

Physical Chemistry, Moore, 1972 Chapter 2

Physical Chemistry, Castellan, l-971 Chapter 7

Fundamentals of Physical Chemistry, Maron and

Lando, L974 Chapter 7

Introductory Physical Chemistry, A. R. Knight,

L970 Chapter 1

Physical Chemistry, Barrow, L973 Chapter 7

PURPOSE:

The purpose of this experiment is to measure the heat of solution of

several salts by a simplified calorimetric procedure.

121
t22 LaboratorY Manual

DISCUSSION:

Astudyofthereferencessho\n/sthattherearetwoheatsofsolution,
,r,-ir",. di f ferentLaL l'teat of ors oLution
The
' when
Lrre integral heat of s ?Lutol d'ii"a evolved
t= ti'*f't absorbed as to grve a
ntegral heat of soluton.s in such, qr""tity of solvent
I mole of solut is dissolved Iile could , fot ""lpf""'-dissolve I mole of solute
specified .on".r.ttaLion. This wur give 0.! mole per cent solution' The
in 200 mores of water. 1
of solution' Again' the more of
heat change *orri-u" rhe inte;;;i hat form a 0'25
sorure courd be dissolvea ir,=i6-*;i;; ;i ;;t;;l rr'i=-wourd
be the integral
mote per cent =oirlior, andvalue trr rreat .rtung;-rr"i.a 1g".t: obtained when 200
the may vary'it-trttt
heat of solution' But or,*[ !it"t f'"l-'" "'Y]d.take such a large
moles of warer are used. pur ""r,a-"rrtio, trrI',tr'in-the addition of l mole of
ouantity of 0.5 mole onry .r, i,Ji.,iii"r.t .t "" concentration' The
Jorute wourd make heat or soluton' I'{e
hear chanse in rhis case *"Ji'il;-tlz"tii)'iJit"t
heat of 3olllion mathematicallv by the
can represent this differenlif uhen L mole of
expression d(AH) /d1,.andsucl't *"-"fine it as #"n"'t o:o,bed. that no appYecable
solute s d.:t.ssoLued t)n ? ?'7'!'.t-a^^'f'Zrullo"
""i;;A; in tLLe coneentv'ation takes pLace'
of certain salts of
Although\^Temayuseanydesil"'dfi,",llconcentrati-on,inthis-experi-
*.."*ri" tfre iiti"l heat^"f
rn
ment we sha,I "f"tion water and I mole
solutions containing 1 mole i'rt Ln 200 *r"= ofare tev'med dilutions
salt in 400 moles of water ' These
-ir," to'"nn'-ilto"" of severar
of 200 and 400 respecrively. integra-h;;t;-oi solution
taken from Bichowsky
salts are given in Table f-f )f .- The 'ui"= given are ' rn this table
Vin*"oL Z"Z;;';"'"'-ig:e
and Rossini, Thermochem"t'u
'n""u{.r";;';;i;tin have a minus sign' This
mosr of the values for the when solution occurs '
means that "";ti;; results

TABLE 14_1

Di lution Q Solution, kJ'mol-l

Salt
200 -26.44
NH 4NO3
400 -1r. 51
CuSO4'5H2O
400 -20 .58
BaCl2 '2H2O
400
+ 8.67
BaCl2 (anhYdrous)
400 -16. rl
MgSo4'7H2O
200 -2L.7L
KI
400 -4'7.40
Na2S 203' 5H2O
 Experiment l4 123

In calorimetric procedures it is necessary to know the heat capacityto

of the calorimeter syltem. By heat capacity we mean the heat necessary proper
change the temperatuie of the calorimeter system, the calorimeter a
and the solutin, by IoC. This can be obtained by introducing measured
the temperature
quantity of heat by electrical means, and then measuring a quantity
rise. ln this expriment, however, we shall introduce is
measured
given in Table LA-L'
of ammonium nitrale, the heat of solution of which
into the calorimeter and observe the change in temperature. Knowing the
quantity of salt introduced, the calories of heat absorbed,can and the tem-
f,eratur drop, the heat capacty of the.calorimeter system be cal-
culated. The exact procedre fr this is given in the section on the
utilization of data.
The procedure followed in this experiment is an adiabaticroom one; that
is, t-cfori*.i"r system is operated sufficiently close to temper-
ature and is so constructed thal the heat loss to or gain from the sur-
roundings is kept vanishngIy sma11

APPARATUS AND CHEMICALS :

calorimeter system as shown in Figure l3-l (see Experiment 13);

Beckmann thermometeri 500-mI volumetri ftask; ammonium nitrate and other
salts selected from Table f4-1.

EXPERI MENTAL PROCEDURE :

' The calori-

The details of the apparatus are shown in Figure rJ-I strrer' The
meter vessel consists of a flqt Dewar flask on a magnetic
Beckmann thermometer is set s6 that the mercury thread reads on the upper
half of the scale when immersed in water at 20oC'

The first step is to determine the heat capacity of t'he calorimeter

t t temperature approxi-
system. a volume f 500 ml of distilled water is read at 30-
mately zAoC is measured into thel;o flask. Its temperature weighed
second intervals until constant 10'OIoC for tree readings' A
to give a dilution of 200, is
sample of ammonium nitrate, sufficient tirred. Temperature readings
introduced, and the mixture is vigorousty
ihe lowst reading is obtained' The
are taker, ..r"ry a0 seconds until ati"a, and the measurement is repeated'
Dewar flask is then emptied t
The same procedure is then carried out with two or more additional
salts.
124 Laboratory Manual

UTI LIZAT' ON OF DATA:

As previously stated, we shall include the volume of the solution as

part of the calorimeter system. Furthermore, we shalt assume that the
eat capacities of the vaiious solutions are the same. The heat capa.city
of the ystem, which we shall represent by the letLer C, is given by the
expression

c=5-"jL (r)
M- x AT-
IJ.

in which v1 is the weight of ammonium nitrate used, M1, is the molecular

weight of'th" salt, e1 is its heat of solution per Tole, and AT, is the
meaiured change in temfierature. Use the experimental data to caltculate
the heat capacitY of the sYstem.

Apply equation (1) to the data for the salt whose heat of solutionthe
you are measuring. 'Solving this equation for Q2, heat of solution of
salt, gives the following:
LTZxCxM, (2)
Q2=
vr2

in which C is the heat capacity of the calorimeter system as determined

with the ammonium nitrate.
Duplicate values for the heat capacity and the heats of solution of
the salts should be obtained with a precision of two within per
parts hundred.
three parts
With good tecfrnique the values obtaied should agree error analysis should
per hundred with those in Table l4-1. An uncertinty
be made.

COMMENTS TO THE INSTRUCTOR:

20o, errors due to heat

If the room temPerature is nearer 25o thanwater
leakage may be minimized by having the initial temperature at 25"C'