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Most commonly. heats of solution are measured with water as the solvent.
Aqueous heats of solution depend not only on the nature of the salute.
but also on the relative amounts of sol u te :md sol ven t. The integral he:n
of solution is defined as the enthalpy change when one mole of sol u te is
dissolved in a definite number of moles of water. far example.
432
Experiments
H:SO~U l -
H:SO~t l -
H:SO~t 1 -
50 H:Ot r'l
H:SO~
= H:SO~( 50 H:O
= H:SO~t
1
1
j.H
.::..H') = -"73.340 J
t4-41
~JI'; = - -
14-:;,
200 H:O
~H" =
-67.030 J
4.940 J
14-J 1
-:ib. i 90 J , ~-1),
l n Figure..:._;. these dar:i :.ire pioned for suifunc :.ic1ci and sorne orhe;
substances. Ir is evident thar the emhalpy change per mole salute ~ve:i
rually becomes constan t. The integral hear of solution ar infinire dilution
is the value obrained when funher dilution causes no further efec~.
Far sodium chloride rhis occurs :n n H:O < 200: far sulfuric acid. J.t
nH 20 > 800.
Experimentally. rhe integral hear of solurion ar infinite dilution :s
found by measuring the integral heats of sol ution ar progressi vely higher
dilutions u mil the enthalpy change per mole of sol u re no longer changes.
Integral hear of solution data pennir calculauon of the integral heat or'
dilution. In this case. the initial stare is a solution of sorne definite concentration. Far example. if Equation 4-.3 is subtracted from Equauon
4-L the result is
~\) =
-.310 J
'laOH
--
- 50 ~
433
Calorimetry
= H:Ot ::' :
'.:-.'! i
lli'.> ( H 20) ~ [ ~: 1 OH - -
.::.ff'.i;
. ~--,)
H . 'i
Far this or any reaction involving ions. :rn l!quai number ot' opposite~y
charged ions must be present. Consequently. there is no way to separare
the contributions of the individual ions represented in the square-bracketed expression. If the he~lt of formation ofjust one ion-any ion-were
known, the contribution of each member or' the pair could be separa tea.
Consequently, it is necessary to adopt the .::onvention that 1he heat ()!.
formation of the hydrogen ion is zero lt :s"' C:
)
:uf . =
1)
~-10 )
H10I e)
= H 20( t)
= ,.' H1(g)
= OH-(aq)
H-( aq)
,.
1
H::(g)
+ - :(g)
:::~ua
;\...;
,...._ l
:uf') = -235.34
'r
;\...;
' ~-1::: )
~)
kJ
:uf
-55.39
f)
1,
w~ = -229 .9 5 kJ
.:-(J)
l ~-1~)
Now that the heat of formation of the hydroxyi ion is knbwn. it can be
combined with thermal data far many cations to determine their heats
of formation. Similarly, the heat of formation of H -( aq). zero by convention. can be used with a variety of metals to find the heats of formation
of their cations by rnea.suring heats of solutions o! metals in dilute acid.
for example.
~u=
-l52.42 kJ
1~-15 )
TABLE 4-1
Heats of Formation at 2SC (kj/mot)
Compounds
..\gO(s)
H10<l')
KOH{s)
ZnS<s)
~r
Cations
~'
-l27.03
-285.84
-425.85
-189.5
Ag"(aq)
W(aq)
K(aq)
zn~raq
Anions
.::.H'
!05.90
Br-(aq)
- !:0.92
o.o
cnaqJ
-!6 7 .~
OW(aq)
2
- (aq)
-:::.9 .95
. 1.3
-25l.::l
- l 52A2
434
Experiments
-152.42 kJ
= llir(Zn~)
~r(Zn: .. ) =
- O- O- O
(4-16i
-152.42 kJ
(4-1'7\
K-) -
= -251.21
.lH? (OH- ) -
14-18\
:JI~' KOH
-H9)
= -55.31 KJ
From a slightly different point of view. we can calculate the heat or" orecipitation of a very slightly soluble substance . ...\gCl 1s1:
AgCl s 1
lli} ( AgCI)
= -127.03
' 4-:o l
1
4-:!l i
12Rt
C=--~ T cai1b
When the current 1 is in amperes. the resistance R. in ohms. and the time
is in second.s. the heat capacity C has units of joules per kelvin. Measurement of the temperature change caused by a sample of g grams and
.\!/ molecular weight gives the heat of solution in joules per rnoie:
l
l l i = C.\!/ ~Tsom
14--:J)
Apparatus
A heat of solution calorimeter consists of a Dewar flask. stirrer, and heater.
A control unit for passing an accurately measured consrant electric current
through the beater and standard resistor is used for measuring the po-
435
C.:tlorimctry
tential developed and the time. A thermistor and \\.neatstane bridge are
needed. and about 20 g potassium nitrate. 1
~~~~~~~~~~~
1 ~51
C~m::;inv,
:: :
E.
1
----"V\/V\/',....-----"IVV'/'.i'r-
R..
-~-
436
Experiments
E1
R1
(-4-25 )
:-..;ow the resistance of the heater Rn may be found if the poten tia!
E" over the heater resistor is measured :
R ., =E"
/
' -'-:6)
e = 3.!:._
.:::.T
, 4-:s 1
= -3..!:.._ =
.::JJh
E,,E,:
R,.:tlJn
14-:9 1
437
Cllorimctry
F
1000.0
;{
) 90.01
1
! .\
:"V
~
....l.L.I
.r o.o !
/
; ~.
.:::. : .!IJ.0
330.0
3:0.0
31 0.0
t)
500
1000
; ~
.:ooo .::soo
.)000
3500
11secl
Fi~ure
: Yellow Spnngs lnsuument Company, lnc .. Box -Ui5. Yellow Springs. Oho -l538i
: SalcntWelch Scientific Company. 9520 Midwcst Ave.. Ganield Heights. Cleveiand. Ohio
Honcywcll. loe.. .WO Bernardo Ave .. '.'li1ountain View. CJ.iifomia 9404 3.
.!.! 125.
438
Experiments
BRIDGE
CALORIMETER
r---------------,1
1
i
CJlorimeter Calorimeter
heater
thermistor
r--~----------------------,
1
:
1
'~!'!:
6K _.
. .
-----------------
Honevwe il
..::
\''
J:.ll \ anoml!!~r
_-,,.
/ :K / ( Jarse
JCIUS!
,...
'
01'.
,,_,- ... - .
,.,..&,
,..
;- : ne
J01us
~---------------------------
CO'-!TROL L'.'IT
,------------------------------------------------::oo
,'"'OK
_
!
'
1
1
~1
6-
- -
o .'.)
1
1
1
1
1
Dummy heater
!- - -
6-.,
o !o
.;C
~rounu
'/
::>-- ~.Hemal
1
1
1
'
~--------.:i:
l
1
power
Pos .
-o.-.
l-~'.)
--'.)
1
Interna! power
S.ta.n dard
resistor
1.0000 l.1
:::: 0.05%
1
1
TB-3
1
1
1
1
IOK
-1 Rs
'.) TB- i
'
~-~--~-~--------------------------------------
resistor. The power to the heater resistor and the timer is switched
on and olf simultaneously with a four-pole. two-throw switch . .--\.
second timer ( not shown) allows measurement of the total run time.
When the power supply is not heating the heater resistor. it is given
a dummy load so that drift is minimized when it is heating the
calorimeter heater resistor. A standard resistor R, is wired in senes
with the heater resistor Ri, . The vo!tage E, over the heater resistor
R,, is reduced to Vh with a voltage divider. and the voitage Es over
the standard resistor Rs is similarly reduced to Vs. The voltages V"
and V5 are measured with a digital potentiometer. which is switched
439
Calorimctry
back and forth between the heater and standard resistors. For the
voltage divider resistor shown in Figure 4-2. the values of E, and
En are calculated from
E =
'
,..
-
.~
11000~-
1000
t:osoor,
500
1 ~-JO
' ~-JI
1. Start the run timer and null the galvanorneter every 50 seconds until enough data are gathered to determine the slope of line
AB.
:!. Open the calorimeter cover. quickly durnp in the sarnple
of K.."O,. and record the run time at the moment of dumping the
sample. Line BC is a nearly vertical line: its ordinate value is the
run time of dumping the sarnple.
3. >f ull the galvanometer again with the bridge fine adjust.
Continue to null every 50 seconds until enough data are gathered
to establish the slope of iine CD.
-1 . Switch the heater switch froin "dummy"' to heater'' and
record the run time at the moment of switching. The heater timer
automatically begins to run as a constant potential is applied to the
calorimeter heater. Heat for l 00 to 200 seconds. While heating,
switch the potentiometer back and forth between the potential over
the standard resistor and the calorimeter heater. They should be
..
440
Experments
C = 265 l V,!;, l /
:>J),,
(4-331
where :'vf is the formula weight. gis the mass of the sample in grams. and
~soin is the change in bridge fme-adjust dial divisions occurring during
the solution process ( line segment BC in Fig. -+~).
Calculate the heat of solution ( kJ /mol) for four samples of pot.assium nitrate. Compare the average with literature values. Determine the
propagated errors.
addition to the solution process. enthalpies of formation. mixing, neutralization, ionization. reaction. displacement. and complex ion formation
have been studied ( Table4-2).
The reaction between silver ion and zinc ( Hill et al .. l 965) is interesting beca use the heat of reaction can also be.measured potentiometrically as described in Experiment 22. The potentiornetric heat of reaction
can then be compared. with the direct calorimetric heat of reaction.
To measure the heat of the reaction between silver ion an :::.inc
with a calorimeter with the sensitivity of the apparatus described in this
~xperiment, use 400.00 mi ! four l 00.00-ml aliquots) of a standard so1ution of silver sulfate about 0.00625 M. Because silver sulfate is the
limiting reagent. the volume of its solution must be accurately known.
but the calorimeter Dewar flask need not be perfectly dry. The optimum
concentration and amount of zinc to be added depend on the apparatus
441
Calorimetry
TABLE 4-2
H~o~
MnO~ =
C:i.C: - HC =
K.Br0 3 + HCI =
!CH 3C0h0 1- NaOH =
6. Enthalpy of comJ>lex ion lonn:iuon: HgC:i- . Cul ~ H:1i P:iu1son c:t
- EnthaJpy of displacemc:nt:
Cu:~ ZnlsJ = Zn~.,.. Cursi 1Charieswonh :ind P::itc:i. ' 1::
Ag..,... Znis\ = Ag(sl ~ zn:" IHill c:t ll.. 1%5)
:l .. : ' ).:
used and are chosen to give ::m adequate temperature change ...\llow :he
solution to come to thermal equilibrium and add about l O g zmc dust.
Ten grams of zinc is a large excess ::md does not need to be accurately
measured. With a large excess of zinc the reaction takes place rapidly
and to completion. Silver nitrate is not a suitable substitute for silver
sulfate. because zinc reacts too s!owly with the silver nitrate. resi.llting in
an inconveniently slow temperature rise ( Hill et al.. l 96 5). However.
silver sulfate d.issolves in water very slowly. so the solution should be
prepared in advance.
Since the reaction is exothermic. it may be necessary to cool the
solution to approx.imately the original temperature befare calibrating the
talorimeter electrically. This is conveniently accomplished by add.ing three
or four pea-sized pieces of solid dry ice to the reaction mixture. When
the original temperature is reached. !et the calorimeter stand several minutes to come to thennal equilibrium before the electricaJ calibration.
Calibrate the calorimeter: calculate the heat of reaction as described
above and compare it with the heat of reaction measured potentiometrically in Experiment 22.
REFERENCES
! . Char!esworth. Y. E .. :.md E. \1. P:nch. '"He:i.t or' Re:i.cuons. Scnooi Sc:ence
Review 13:256. 1932.
:. Oever. H. L.. "Heat of Precipitation. I Chem: Educ. 38:470, 196 l.
3. Hill. O. L.. S. J. H. Moss. and R. L. Strong, 'Heat of Reaction in A.queous
Solution by Potenriometry and CJ.lorimetry," J. Chem. Educ. 42:541. 1965.
4. Lewis. G. ~ . and M. Randall. revised by K. Pitzer and L. Brewer. Thermadynamics. 2nd ed., McGraw-Hill, New York. 1961.
S. Mahan. B. H .. "A Simple Ice Calorimeter: J. Chem. Educ. 37:634. t 960.
442
Expcriments
6. Matthews, P. G., "A Simple Experimental Test ofHess's Law," School Science Review 45: 194, 1963.
7. Miller, J. G., A. l. Lowell, and W. W. Lucasse, "Calorimetric Studies of
'.'ieutralization Reactions," J. Chem. Educ. 24: 121. l 94i.
3. Neidig, H. A .. H. Schneider. and T. G. Teates. "Thermochemical Investigations far ;:i First-Year College Chemistry Course. J Chem. Educ. 42:26-3 l.
1965.
9. P:mison. D. B.. J. G. Miller, and W. W. Lucasse. "Simplified Calorimetric
Studies of Yarious Types."' J. Chem. Educ. 20:319. 1943.
iO. Rossini. F. D .. ed .. Experimental Thermochemzstry. Interscience. >iew York.
1956.
l l. Stunevant. J. M .. in A. Weissberger. ed .. Tt!chnwue o(Orf?antc Chemzsrry
vol. l. pt. l. Interscience. New York. 1959.
l :. Stunevant. J. \i1.. in A. Weissberger. c:d .. Tecnnzques q( Chemisir'.'. voi. '..
pt. 5. Wiley-lnterscience. New York. 197 l.
l 3. Zaslow. B.. "The Heat of Mixing of Organic Liquids.'" J Czem. Educ. 37:
578. 1960.