Simple Heat Flow Measurements

A Closer Look at Polystyrene Cup Calorimeters

Lawrence N. Ngeh, John D. Orbell, and Stephen W. ~lgger'
Department of Environmental Management, Victoria University of Technology, St. Albans Campus, McKechnie Street,
St. Albans, 3021, Australia
The educational literature contains many papers relat- suitable for heating a 400-mL beaker containing about 200
ing to the construction andlor use of calorimeters for teach- .,
mL of water: a maenetic stirrer and "flea" to stir the con-
ing purposes. Examples of these include an isobaric calo- tents of the cnlonmeter; a ceramlc electric jug I 1-L capac-
rimeter for determining the calorific content of simple ity,; a digital multimatcr (Escort, model EDM-1631.
foodstuffs (I), a n isothermal calorimeter for measuring
heats of vaporization (21, a differential microcalorimeter The Experiments
for studying reaction enthalpies in solution (31, a low-cost
labyrinth calorimeter (41,and various other calorimeters Simple Calculations Relating to-HeatFlow
that have been designed for studying reactions in solution
(5-7). Furthermore, a most elegant paper describing both The original idea that heat is a measurable quantity that
the theoretical derivation of the heat capacity of metals mav flow from one bodv to another has been attributed (16)
and a calorimetric ex~erimentto measure this quantitv to <he work ofJoseph 6lack that was published as long ago
has appeared in the educational literature (8,. as 1803. Under conditions of constant Dressure, the auan-
More recentlv, the use of -polvstyrrne foam cups as "calo- tity of heat, q, that is transferred to or From a body ofmass
- - m is related to its temperature change AT by the familiar
rimeters" in ;hdergraduate teaching laboritories has
proven to be a most economical and convenient means by expression:
which to introduce students to elementary thermochemi- q = CpAT (1)
cal measurements. Many modern textbooks (9-11) and
laboratory manuals (12,13) describe experiments in which, where C, is the specific heat capacity of the body at con-
typically, a polystyrene cup is used as a calorimeter to stant pressure. If a quantity of heat is transferred from one
measure the heat capacity of a metal or the enthalpy body to another, then eq 1can be used to derive the expres-
change associated with a chemical process. A few experi- sion:
ments that involve the construction and use of polystyrene
cup calorimeters in undergraduate teaching also are de-
scribed in the mainstream educational literature. These where C1and C2are the specificheat capacities a t constant
include the measurement of the heat of sublimation of dry pressure, T I and T z are the initial temperatures of the re-
ice (14) and the construction and use of .~olvstvrene
- - micro- spective bodies, and T is the final temperature attained by
calorimeters (15). the system when the process of heat flow is complete and
To our knowledge, despite the significant number of pa- thermal equilibrium is reached (16).
pers in the educational literature devoted to calorimetry, Equation 2 can be used to calculate the specific heat ca-
the elementary topic of heat flow and the simple calcula- pacity of a substance (e.g., a pure metal) from calorimetric
tions relating to it have yet to be addressed formally. This measurements provided that the specific heat capacity of
article describes a sequence of experiments based on the the calorimeter and its contents are known. Indeed, the
use of polystyrene cup calorimetery together with simple specific heat capacities of many pure metals can be deter-
computer programming that we have found to be most ef- mined satisfactorily in this way using polystyrene cup
fective in illustrating the principles of heat flow to junior calorimeters and is an exercise commonly associated with
undergraduate students. the use of such devices. We have incorporated an experi-
ment along these lines as the final step in the sequence of
The Apparatus heat flow experiments described herein.
The experiments are performed using as "calorimeters", A much sim~ler.althoueh related. ex~erimentinvolves
200-mL polystyrene drinking cups that can be obtained investigating (he effect of idding hotwaiw to cold water in
readily from any supermarket; mercury-in-glass ther- a. ? . CUD calorimeter 117,. If a known masfi of hot
oolvstvrene
mometers (0-110 f 0.1 "C, -10-50 f 0.05 "C ; a hotplate water (mz) is added to a known mass of cold water (ml)
contained within the calorimeter and no heat is absorbed
by the calorimeter, then the temperature, T, reached after
I Author to whom correspondence should be addressed. thermal equilibrium is given by eq 3. This equation is de-

Volume 71 Number 9 September 1994 793

 40

-
E
I-
35

30

25
40 50 60 70 80
T2 (OC)
Figure 1. Plot of the equilibrium temperature, T, versus the initial tem- Fdg~re3 Plotsof Tvers-s m2der ved from tneorellca oata generated
perature. T2,of 50 g of hot water that was added to a polystyrene cup oy tne compder program given in F gdre 2 Jsmg T, = 20 'C, T 2 = 80
calorimeter originally containing 100 g of water at 22.5 "C (room 'C and va Les of m, of (a, 50 g (b, 200 g, (c, 500 g. ano to 1000 g
temp.).Linear least-squares regression coefficient, ? = 0.99.
without havine to make a correction for the heat absorbed
by the calorimker itself (9, 13, 15).
REM: Program "TempCalc" I t is possible to reinforce the student's understanding of
the derivation and use of eq 3 by reference to a simple com-
puter program (see Fig. 2) that generates the coordinates
(T, m2)for given values of ml, TI ,and T2. The student may
be asked simply to examine and use the program or, alter-
9 . . -
nativelv. the oroeram could be set a s a simole . promam-
ming exercise. The data produced by the program can be
& -

REM: Set initial mass and mass increment

m2=0 used to construct a familv of curves (see Fie. 3) all of which
dm2=5 show the expected asymptotic approachutoward T2, the
temperature of the hot water added to the calorimeter a s
REM: Calculate and display (m2,T) coordinate: the quantity of the latter, mz, approaches infinity. Plots
FOR i=l TO 30 such as the ones shown in Figure 3 also mav be used to
m2=m2+(i-l)'dm2
T=(ml'Tl +m2'T2)/(ml +m2) c o n i i i experimental data or help in the choice of other
PRINT USING "####";m2; conditions under which the students may wish to perform
PRINT" ": the experiment.
PRINT U S ~ N G"##.#";T For those students who are mathematically inclined, eq
.NEXT i~

3 lends itself to a practical application of the familiar

STOP L'HBpital rule:
I I
Figure 2. A simple BASIC computer program that may be used to
aenerate the coordinates (.T., mil
-. in accordance with eg 3 for given
h u e s of m,, T, .and T2.
where fdmd and fdm2) are the numerator and denominator
rived from eq 2 for the case where the specific heat capaci- of eq 3 &&ivel~, and firm2, and f;(m2 represent the first
ties are equal: denvnti\.rs of thc respenwe functions with respect tom?.
T = ~ I T+ImzTz Measuring the Specific Heat Capacity of Water
m1+mz (3)
In order to use eq 2 to calculate the specific heat capacity
As a n introduction to the concept of simple heat flow a of a pure substance, it is necessary to know the specific
series of preliminary learning experiments is conducted heat capacity of a reference substance (usually water) that
where each experiment involves measuring the equilib- is contained within the calorimeter. We have found that it
rium temperature, T, following the addition of a known is possible to obtain a remarkably good value of the specific
quantity of hot water to a known quantity of cold water, heat capacity of water from measurements that can be
the latter being contained originally in a polystyrene cup made using a 1L ceramic electric jug, a common household
calorimeter. The measured values can be compared with item, a s a "calorimeter". The use of a ceramic electric jug is
those predicted by eq 3. A major advantage of this ap- recommended in preference to, say, one made from metal
proach is that calculations can be performed without the because the former has superior thermal insulating prop-
prior knowledge of specific heat capacity data. erties.
Figure 1is a plot of the equilibrium temperature, T, ver- Despite the obvious fact that a n electric jug (albeit ce-
sus the initial temperature, Tz, of 50 g (m2) of hot water ramic) is bv no means a n exceedinelv .. . precise
. thermo-
that was added to a polystyrene cup calorimeter originally chemical instrument, we bdieve that the method has con-
containing 100 g (ml) of water a t TI = 22.5 "C (room tem- siderable merit in that it enables a satlsfacton valueof the
perature). The gradient of the linear least-squares regres- specific heat capacity of water to be obtained directly with-
sion line in the plot compares favorably with the theoreti- out having to correct for the heat lost to the "calorimeter".
cally expected value of 0.33. This clearly demonstrates the ~urtherm&e,the method demonstratt.~1,) the student an
high degree of precision that can be achieved with a poly- application ofthermodynamic3 that is related to the every-
styrene cup calorimeter over a wide temperature range day world.

794 Journal of Chemical Education

 The student is asked to measure, with a digital multime- Specific Heat Capacities Of Various Metals Determined
ter, the resistance, R, of the heating element when the jug Using an Expanded Polystyrene Cup Calorimeter
is disconnected from the mains (a typical value ofR is 36.2
ohm for a nichrome heating element rated a t 1600 W). A Metal Cp(expt.)x 1W2J tC1k g 1 Cp(litJax 10" J IC' kg-'
known quantity of water (typically 1.0 L) is added to the
jug and the initial temperature (TI) recorded. The jug is Al 9.0 0.5 9.0
connected to the mains (voltage V)and the time, t, re- CU 3.8f 0.2 3.9
quired to bring the water to the boiling point (Tz) is meas-
ured. If the density of water is assumed to be 1.0 kg L-', Fe +
4.4 0.3 4.5
then the mass of water in the jug, m, can be determined Zn +
3.9 0.3 3.9
accordingly, and the specific heat capacity of water can be 'Literature values were obtained from Ref. 18.
calculated from:
4. The specific heat capacity of the metal (C2)is calculated
from eq 2 where the specific heat capacity of water (C1)is
that determined from the orocedure eiven in the orevious
where the quantity of heat, q, required to boil the water is experiment.
assumed to be equal to the electrical energy, VIt, dissi- The table lists typical specific beat capacity values that
pated in the jug and the specific heat capacity is assumed are obtained using this method together with the corre-
to be a constant over the temperature range. Ohm's law is sponding literature values (18).
used to eliminate the current, I, from the eauation.
Using this method a value of C, = (4.25 f 009) x lo3J K-' Conclusions
k e d is obtained that is in good aaeement with the - eener-
aiiy accepted value (18)of4.18 x G3JK-' kg-'. The experi- Polvstvrene
" cun calorimeters offer a most economical
mentallv determined value of C. is used in the subse~uent and convenient means by which to demonstrate to junior
experiments. u n d e r a a d u a t e students the fundamental ~ r i n c i ~ l eofs
As a n extension of this simple experiment, students can heat $ow and calorimetry. I t is our experience that the
be asked to calculate the cost of boiling the water in the jug s i m ~ l eseauence of ex~erimentsand the associated calcu-
having firstly determined the price of electricity per kW h lations presented above provide the student with a logical
from a recent electricity bill. The cost, c, of boiling the develo~mentof the t o ~ i and c a ~reliminarv
. a ..
~ ~ r e c i a t i of
on
water is given by: the reievance of the-odpamks.
The e x ~ e r i m e n t svield remarkablv eood values of the
C =
Vtp measurei quantities directly withou"t ;he need for deter-
3.6 x 1 0 6 ~ (6) mining calorimeter constants. More refined calorimetric
determinations can be discussed and performed by stu-
wherep is the current local price of electricity per kW h. dents in later years when they presumably have a more
complete understanding of the elementary principles.
Measuring the Heat Capacities of Various Metals
The specific heat capacities of aluminium, copper, iron, Literature Cited
and zinc can be determined satisfactorily using a n ex-
panded polystyrene cup calorimeter. A suitable procedure 51,829-830.
2. Amett,E. M.;Oaneea,D. J Chem. Educ 197.5,52,269-271.
which will produce a significant temperature change (in 3. Bafler N.: Letellier P.: Labbe. J. P. J. Chem. Educ 1976.53.597dW
. .
the range 4-8 " C )in the calorimeter is a s follows: 4. ~brre&rnez. L. A:; &as-~kilar, A. J. Chem Educ 1991,68,671-673.
5. Bartle, K D.; Oabome, P M . J. Chem. Educ. 1973.50.637.
A 2 x 2 x 2 cm block of metal (m2)is thermally equilibrated 6. Railen. D. A,:Fung,B. M.;Chrisfian,S.D. J Chem. Educ. 1388.65.932-933.
in a beaker of boiling water and the initial temperature of 7. Bigger, 8. W; Meilak, G. b Verity, B. J Chem. Edue. 1991,68,52&530.
the metallic block (TZ),is recorded accurately using the 8. Shigeiahi, R.A. J. Chem. Edue lW9,56.59-61.
0-110 OC thermometer. 9. Miller, F M. ChemislrySlruclum and Dynamics, int, student ed.; Maraw-Hill:
New Ymk. 1986. o 72.
-
60.0mL of water (ml) at room temperature is placed in a
~ ~

10. Oxtoby, D. W.: Naehtriels, N. H. Principks d f ~ & m Chemistry, 2nd ed.: Sanders:
polystyrene cup and gently stirred with a small magnetic Philadelphia, 1990; p 261.
"flea".The temperature of the water in the cup (TI)1s re- 11. Chang, R. Chemisfn 4th ed.:MeCraw-Hill: New York, 1991: p 230.
12. hon. E. R.; Ellis. G. L.; Doyle, L.; lvanm J. ;Percival. S. Foundations ofchemistry-
corded accurately using the -10-50 "Cthermometer. Lobamlory Manual, 2nd ed.; Holt, Rimhart and Winston: Tomnto, 1991:p 84.
The metallic block is removed quickly from the boiling 13. Robem.J. L., Jr: Hollenberg, J. L.; Po8tma.J. M. Genemi Chemistry m iheLobom-
water using large plastic tweezers and placed in the poly- tory, 3rded.; W H. Freernan:NewYork, 1 9 9 1 : ~151.
-
stvrene euo calorimeter without inhibitine the stirrine
motlan of the "flea".The temperaturr of the system 17: IS
14. Burgstahler,A. W; Bricker, C. E. J. Chem. Educ. 1991,68,332333.
15. Bmuwer, H. J. Chem. Educ. 1991,68,A171.A181.
recorded usmg the -10-50 'C thermometer ancr thermal 16. Mwre, W. J. Physiml Chemistry, 5th ed.; Longman: Esser, 1972:p 29.
17. Silbeman,R. G J. Chem. Educ 1982.59.229.
equlllbnum ise3tablished. Equilibrium isatmined within 18. Hondbmk of C h i - f r y and Physfcr 72nd ed.; Lide. D. R., Ed.; CRC h a s : Boca
approximately 15 s. Raton. 1991.

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