See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/299398088

Coffee Cup Calorimeter Heat Loss Correction

Article  in  The Chemical Educator · January 2016

DOI: 10.1333/s00897162683a

CITATIONS READS
0 7,005

2 authors, including:

John Young
Saint Mary's University
16 PUBLICATIONS   17 CITATIONS   

SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Autotitrator titrant dispenser hydrodynamics View project

All content following this page was uploaded by John Young on 24 February 2018.

The user has requested enhancement of the downloaded file.

 Chem. Educator 2016, 21, 53–62 53

Coffee Cup Calorimeter Heat Loss Correction

John C. O’C. Young*

Department of Chemistry, Saint Mary's University, Halifax, Nova Scotia, Canada, B3H 3C3,
john.young@smu.ca
Received November 5, 2015. Accepted March 9, 2016.

Abstract: The ubiquitous and imperfectly insulated coffee cup calorimeter is shown to be subject to significant
rates of heat transfer through its polystyrene foam walls to their external surroundings, invalidating the
commonly employed calorimeter constant heat loss correction procedure. The alternative post-reaction
temperature trend extrapolation procedure for heat loss correction is examined and an enhanced version is
validated in a determination of the heat of solution of sodium hydroxide in water.

Introduction external surroundings and little or no heat storage in the walls

An interesting intellectual challenge with practical
pedagogical implications is to try to obtain reasonably accurate
physical data from relatively primitive pieces of apparatus, in
the present instance the coffee cup calorimeter. More
sophisticated calorimetric systems, in which the primary
emphasis is on delivering data as accurately and expeditiously
as possible, tend to conceal the principles and premises
underlying their built-in operating and data processing
procedures.
Coffee cup calorimetry is reviewed in most general
chemistry textbooks and offers an informative, low-cost
introduction to thermochemistry that has been widely explored
experimentally at varying levels of sophistication in
undergraduate university laboratory programs.
In our second year physical chemistry laboratories we make
use of more advanced commercial, computer-interfaced
solution and bomb calorimeters. However, in our first year
general chemistry laboratory programs, our students employ
coffee cup calorimeters to investigate the exothermicity of the
solid sodium hydroxide-hydrochloric acid reaction and to
make a Hess’s Law-based determination of the heat of
combustion of magnesium metal.
The matter of correction for heat loss from the coffee cup
calorimeter is reportedly treated in one of three ways: it is
assumed to be negligible, or to be significant but entirely
retained within the walls of the calorimeter, or largely to pass
through the walls of the calorimeter to its surroundings and be
quantified by back extrapolation of the contents temperature
trend in the post-reaction period. Each of these alternative
procedures will be considered.
Negligible Heat Exchange with the Calorimeter’s
Surroundings
A coffee cup calorimeter is an unsophisticated apparatus
and the results obtained with it are not highly accurate,
largely because some heat is transferred to or from the
surroundings [1].
In their treatments, general chemistry textbooks mostly
disagree with this assessment and explicitly state or implicitly
assume little or no heat transfer from the calorimeter to its
of the calorimeter, which are perhaps acceptable assumptions if
the sole purpose of the exercise is to present a simplified
introduction to thermochemistry.
In their treatment of coffee cup calorimetry, Radel and
Navidi [2] contend that “Because the thermal insulation is
extremely good, essentially no energy transfer can occur to or
from anything outside the calorimeter”. Similarly, Hill and
Petrucci [3] claim that “its very low heat capacity allows us to
neglect the small amount of heat gained by the Styrofoam and
the foam is a good thermal insulator that permits very little
heat to escape from the calorimeter”. Elsewhere, Petrucci et al.
[4] state that “Styrofoam is a good insulator, so there is little
heat transfer between the cup and the surrounding air. We treat
the system – the cup and its contents – as an isolated system”
(emphasis in the original). According to Tro [5], “Since the
insulated (coffee cup) calorimeter prevents heat from escaping,
you can assume that the heat gained by the solution equals that
lost by the reaction.” Referring to the customary double cup
arrangement, Atkins and Jones [6] suggest that “The outer
polystyrene cup acts as an extra layer of insulation to ensure
that no heat enters or leaves the inner cup,” although, in fact,
the addition of the second cup would less than halve the heat
flow rate through the first cup. Brady and Senese [7] opine that
“A reaction in such a calorimeter exchanges very little heat
with its surroundings, particularly if the reaction is fast.” As a
practical matter, typical experiments involving the dissolution
of a soluble solid or the determination of the specific heat of an
insoluble solid take place fairly slowly. Also referring to the
double nested cup configuration, and amongst others, Moore et
al. [8] assert that “Because (its) thermal insulation is extremely
good, essentially no energy transfer can occur to or from
anything outside the calorimeter.”
A necessary condition for no heat transfer to occur between
a coffee cup calorimeter and its surroundings is that its external
wall surface must remain at the surroundings temperature. It
would appear that none of these authors has ever held a
doubled cup of hot coffee or asked for a sleeve.
Heat Loss Retained within the Walls of the Calorimeter
This behavioral model does admit of appreciable heat loss
from the contents of the calorimeter but assumes that it is

© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf

54 Chem. Educator, Vol. 21, 2016
entirely absorbed and retained within its walls, therefore again
requiring that the external wall surface temperature remains at
that of its surroundings and also that the post–reaction
temperature of its contents remains constant.
It is exemplified by the College Board’s “AP Chemistry
Lab: Calorimetry” procedure for determining the value of the
so-called “calorimetry constant” of a plastic foam calorimeter
[9], which is based on assumptions that this type of calorimeter
does not conduct heat well but does absorb some heat, and that
“The calorimetric constant represents what portion of the heat
flow of the process done in the calorimeter goes into the
apparatus itself rather than affecting the temperature of the
heat sink (the contents of the calorimeter). Once the
calorimetric constant has been determined for a given
apparatus, the value determined can be applied whenever that
calorimeter is used in subsequent experiments,” in effect that it
is a universal constant that may be applied to correct for heat
loss from the contents of the calorimeter under all
circumstances.
The AP procedure for determining the value of the
calorimetric constant has been described as follows [9]:
A measured quantity of cold water is placed in the
calorimeter to be calibrated and is allowed to come to
thermal equilibrium with the calorimeter. Then a measured
quantity of warm water is added to the cold water in the
calorimeter. Since the energy contained in the warm water
is conserved, we can make the following accounting of the
energy:
qwarm water = – (qcold water + qcalorimeter)
(in which) . . . the amount of heat absorbed by the
calorimeter can be found by
qcalorimeter = Ccalorimeter Δt
in which ∆t is the temperature change undergone by
calorimeter, and Ccalorimeter is the calorimetric constant,
which represents the number of kJ of heat required to
warm the calorimeter by 1 oC.
By this procedure which assumes no heat loss from the
calorimeter to its surroundings, if a mass mh of hot water at
temperature th is added to a mass of cold water mc at
temperature tc resulting in final temperature tf, the value of the
calorimetric constant is calculated as
Ccalorimeter = [mh (th – tf) – mc (tf – tc)] / (tf – tc)
which the procedure envisages is the amount of heat required
to raise the temperature of the calorimeter and implicitly its
stirring and temperature measuring accessories by 1 oC, that is
their combined heat capacity.
Also referring to this procedure, Whitten et al. [10] state that
the amount of heat released by an exothermic reactions is equal
to the amount of heat absorbed by the test solution plus the
amount of heat absorbed by the calorimeter, indicating that the
latter “ . . . is sometimes expressed as the heat capacity
(emphasis in the original) of the calorimeter, in joules per
degree. The heat capacity of a calorimeter is determined by
adding a known amount of heat and measuring the rise in
© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf
John C. O’C. Young
temperature of the calorimeter and the solution it contains.
This heat capacity of a calorimeter is sometimes called its
calorimeter constant” (ditto), and suggest a value of 24 J oC–1
for a lidded, double polystyrene foam cup calorimeter.
Amongst others, similar calorimeter constant procedures
have been proposed by Stankus and Caraway [11], Postma et
al. [12], Di Domenico (13) and Greco et al. [14], and also by
Nelson and Kemp [15] who added 50.0 ml of water at 37.92 oC
to 50.0 ml of water at 20.91 oC in a coffee cup calorimeter and
obtained a final temperature of the combination of 29.11 oC,
indicating a calorimetric constant value of
{50.0 4.18 (37.92–29.11) –
50.0 4.18 (29.11–20.91)}/(29.11–20.91) = 15.5 J oC–1
If 100 ml of liquid were placed in a 150 ml polystyrene
coffee cup, the mass of the wetted portion of the cup would
amount to 1.00 g. Coffee cups are made from expanded
polystyrene foam which has a specific heat of 1.3 J g–1 oC–1. A
4.0 g magnetic stir bar would have a heat capacity of
approximately 2.0 J oC–1 while that of the immersed portion of
a steel jacketed thermistor is uncertain but should somewhat
exceed 2.0 J oC–1. Based on these assumptions the heat
capacity of a double cup calorimeter system is estimated to be
only 2 1.0 1.3 + 2.0 + 2.0 ≈ 7 J oC–1 The larger values of 15.5
and 24 J oC–1 noted above indicatet variable heat losses through
the walls of the calorimeter greater than can be stored within
them.
It is implicit in the calorimetric constant procedure that heat
transfer can take place into the walls of the calorimeter but not
through them to their surroundings, in which case, given
sufficient time and an exothermic reaction in the calorimeter,
the walls would be heated to a uniform temperature throughout
equal to the post-reaction temperature of the contents of the
calorimeter. For this to occur, the cupped calorimeter would
have to be completely surrounded by a perfect insulator and
atmospheric air does not qualify and permits significant heat
loss to occur through the walls of the calorimeter to their
surroundings.
The magnitude of heat transfer through the walls of the
calorimeter may be estimated by examining their thermal
resistance.
The entrapped still air in polystyrene foam makes it an
excellent insulating material with a thermal conductivity of
only (k =) 0.033 watt m–1 oC–1 but the wall thickness of (l = )
0.0020 m provides insufficient thermal resistance to prevent
significant heat transfer through the cup wall(s).
This thermal resistance provided by n (= 1 or 2) cups is
given by
R = 1 / hi + n l / k + 1 / he ≈ n l / k + 1 / he
in which hi and he represent the internal and external boundary
layer heat transfer coefficients, the former for a liquid layer
being much smaller than that for the air layer at the external
surface of the calorimeter (1 / hi << 1 / he).
Experimental data presented in Figure 4 of a study by Totola
et al. [16] of natural convective heat transfer from a vertical
cylindrical tube to quiescent atmospheric air surroundings
show a heat transfer coefficient of 9.4 W m–2 oC–1. Assuming
this value for he, the thermal resistance relationship becomes
Coffee Cup Calorimeter Heat Loss Correction
R = 0.0020 n / 0.033 + 1 / 9.4 m2 oC W–1
corresponding to a heat loss rate through the calorimeter wall
of
dq / dθ = A ( ti – te )/R = A ( ti – te ) / (0.0020 n/0.033 + 1/9.4)
= A ( ti – to )/(0.0020 n/0.033) = A (to – te)/(1 / 9.4) watts
in which te represents the temperature of the surrounding air
environment and ti and to the external and internal surface
temperatures of the calorimeter wall, the latter being assumed
to be equal to that of the contents of the calorimeter.
From this relationship, the temperature of the external
surface of the calorimeter
to = [ (1.76 / n) ti + te ] / [ 1.76 / n + 1 ] oC
For a liquid temperature and hence the inner wall
temperature of say ( ti = ) 70 oC and a calorimeter surroundings
temperature of say ( te = ) 20 oC, the outer wall temperature is
estimated to reach to = 52 oC for a single cup calorimeter ( n =
1) and 43 oC for a double cup calorimeter (n = 2). Thus double
cupping should only reduce the heat loss rate by 100 [1 – ( 1 /
2 ) ( 70 – 43 ) / ( 70 – 52 )] = 25 %.
If a 150 ml coffee cup is filled with 100 ml of liquid, the
area of contact between the liquid and the inner cup wall will
be approximately 100 cm2 (A = 0.0100 m2), and the heat loss
rate will be
dq / dθ = A ( ti – to ) / (0.0020 n / 0.033)
= 0.0100 ( 70 – to ) / (0.0020 n / 0.033)
= 2.97 watts for n = 1 and 2.22 watts for n = 2
The corresponding initial rate of decrease of the temperature
of the contents of the calorimeter, assumed to be water for
which Cp = 4.18 J g–1 oC–1, would be 0.43 oC per minute for n
= 1 and 0.32 oC per minute for n = 2.
Limited heat storage capacity and significant heat flow
through the walls of the coffee cup calorimeter invalidate the
calorimeter constant heat loss correction procedure. Heat
storage and heat transmission have differing temperature
dependencies that make the computed “calorimeter constant” a
variable whose value will depends on the particular choice of
the hot and cold water temperatures and their mass ratio. Its
value will also be time dependent. It is not therefore “ . . . a
universal constant that may be applied to correct for heat loss
from the contents of the calorimeter under all circumstances”
[9].
The calorimetric constant approach was perhaps
appropriated from bomb calorimetry, for which it is
appropriate because that type of calorimeter together with its
surrounding insulated, closed water tank closely approximate
an isolated system.
The Post-Reaction Temperature Trend Procedure
This method requires only somewhat extended monitoring
of the contents temperature versus time trend in the
calorimetric experiment and implicitly assumes that heat
© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf
Chem. Educator, Vol. 21, 2016 55
transfer through, rather than storage in, the walls of the
calorimeter is the dominant but not the sole cause of heat loss
from the contents of the calorimeter.
Illustrative of this procedure, an edited version of a
thermogram obtained by Citano [17] is shown in Figure 1. In
this procedure, the post-reaction temperature trend was
extrapolated back to the time at which the reaction was
initiated and the difference between the extrapolated
temperature at that time and the temperature at the start of the
reaction period was then multiplied by the heat capacity of the
solvent to obtain an estimated value of the heat of reaction. In
this example, the heat loss correction amounted to (100 (34.8 –
34.0) / (34.0 – 24.0) =) 8.0% for a reaction that took place over
a modest temperature range in a short period.
This linear extrapolation procedure which has been widely
adopted [18-26 amongst others] is open to criticism because it
makes no allowance for difference between the heat capacities
of the solution and its solvent or for heat delivery from the
cooling calorimeter and its accessories and, more importantly,
it implicitly assumes that the rate of heat loss due to cooling
throughout the reaction period is equal to the rate observed at
its end when the solution temperature is at its maximum value.
Generally, the temperature of the system at the start of the
reaction will be close to ambient in which case the heat loss
rate will be essentially zero at that time, suggesting that the
temperature correction for heat loss should be approximately
half that illustrated in Figure 1, that is 0.4 rather than 0.8 oC.
In the following experimental investigation, an enhanced
version of the post-reaction temperature trend heat loss
correction procedure was developed to correct for these
deficiencies and its efficacy assessed in a determination of the
standard heat of solution of sodium hydroxide in water at
infinite dilution.
Experimental
Using the experimental setup illustrated in Figure 2,
temperature measurements of the contents of the calorimeter
and of its external surroundings were made at one second
intervals during cooling of a hot water sample and during the
dissolution of a range of measured quantities of sodium
hydroxide solids in deionized water initially at room
temperature in a 150 ml, lidded, vented, polystyrene foam,
double coffee cup calorimeter. (In an unreported study, the use
of a vented lid was observed to decimate evaporative heat
loss). The calorimeter was inserted for stability into a 250 ml
glass beaker and fitted with a magnetic spin stir bar and a
thermistor temperature sensor and a second sensor monitored
the air temperature in the vicinity of the external surface of the
beaker.
Temperature measurements were made with a pair of
Vernier Model TMP-BTA thermistor probes and relative
humidity measurements were made with a Vernier Model RH-
BTA probe, and the data from these sensors were delivered via
a LabPro A/D interface to Vernier’s Logger Pro data analysis
and presentation software program version 3.8.6.4 [27].
By monitoring the decrease in temperature over time of a
hot water sample, a relationship was established between this
temperature trend and the rate of heat loss from the calorimeter
to its external surroundings. This relationship was then applied
to an experimental determination of the standard heat of
solution of sodium hydroxide in water at infinite dilution,
56 Chem. Educator, Vol. 21, 2016
Figure 1. An exothermic thermogram.
Figure 2. Calorimeter system and data logging instrumentation.
which was compared with the reported reference value for this
reaction.
Results and Discussion
Contents Temperature Correction for Heat Loss. If
conduction through the walls of the calorimeter is the
dominant cause of heat loss from the imperfectly insulated,
lidded coffee cup calorimeter, it should closely follow
Newton’s Law of Cooling and occur at a rate approximately
proportional to the difference between the temperature of the
contents of the calorimeter and that of its external
surroundings.
To test this proposition over a higher and more extended
temperature range than is commonly encountered in
calorimetric experiments, measurements of the temperature of
a 100 g deionized water sample were made at one second
intervals over a cooling range from 80 to 50 oC and these data
are plotted in Figure 3.
For a hot water sample temperature t at time θ, the
instantaneous rate of heat gain by the surrounding environment
(env) due to heat loss through the walls of the calorimeter may
be expressed as
dqenv / dθ = U A (t – tenv)
in which A represents the wetted wall area of the calorimeter
and U the overall heat transfer coefficient whose value will be
a constant if Newton’s Law of Cooling is obeyed . In terms of
the change in temperature of the calorimeter, its accessories
and contents together having a heat capacity w Cp
© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf
John C. O’C. Young
dqenv / dθ = – w Cp dt / dθ = – w Cp d(t – tenv) / dθ
if the surroundings temperature tenv remains constant.
Therefore
d(t – tenv) / (t – tenv) = – U A / (w Cp) dθ
Integrating this relationship assuming the value of U to
remain constant
ln(t – tenv) = – U A / (w Cp) θ + a constant = – k θ + a constant
This relationship plotted in the lower part of Figure 3 for the
hot water data set shows slight but distinct concavity.
Replacing the linear regression shown with a quadratic
relationship would reduce its root mean square error (rmse)
value from 0.0072 to 0.0016. However this value of 0.0072 for
the linear data set corresponds to an error of only 0.21% at an
intermediate ordinate value of 3.5, and this error would be
smaller for a lower, narrower temperature range than 80 to 50
o
C. Constancy of the value of the overall heat transfer
coefficient U and therefore accordance with Newton’s Law of
Cooling may therefore reasonably be assumed.
In place of the simple linear extrapolation of the post-
reaction temperature trend back to the reaction starting time
illustrated in Figure 1, accordance with Newton’s Law of
Cooling provides the basis for an enhanced procedure for
correcting for the heat loss occurring during an exothermic
reaction taking place in a coffee cup calorimeter (or for the
heat gain in the case of an endothermic reaction).
This procedure begins with an evaluation of the functional
group k = U A / (w Cp) from the slope of a plot of ln(t – tenv)
versus time θ in the post–reaction period in which the
downtrend in the temperature of the contents of the calorimeter
is entirely due to heat loss. Illustrated in Figure 4, an
exothermic reaction in which a mass of 7.527 g of sodium
hydroxide was dissolved in 50.053 g of deionized water
initially at a temperature of 22.55 oC yielded a value of k = U
A / (w Cp) = 0.0224 minutes–1.
For a calorimeter contents temperature t at time θ, the heat
loss in the time interval
θ to θ + dθ = U A (t – tenv) dθ
and the heat release by the exothermic reaction in this time
interval
dq = w Cp dt + U A (t – tenv) dθ
= w Cp d(t – ti) + U A (t – tenv) dθ
= w Cp d(t – ti) + k w Cp (t – tenv) dθ
= w Cp d(tc – ti)
in which tc represents the contents temperature corrected for
heat loss. The heat release over the period θi to θ
θ
q  w Cp  t c – t i   w Cp  t – t i   k w Cp θ (t – t env ) dθ
i
Coffee Cup Calorimeter Heat Loss Correction Chem. Educator, Vol. 21, 2016 57

Figure 3. Water sample cooling temperature profile.

Figure 4. Exothermic reaction temperature and heat loss correction profiles.

from which the corrected temperature of the contents at time θ chosen time intervals Δθ in the spreadsheet section of the
data logging and analysis program.
θ  When these temperatures have stabilized, add the solute
tc  t  k θ (t
i
– t env ) dθ or second solution, also at or close to the temperature of
the surrounding environment. Replace the lid and
j=m
t k θ  (tθi+jθ – t env ) : m   – i  / 
continue measurements for at least 5 minutes after the
peak temperature reading is observed.
j=1
 Prepare a calculated data column in the spreadsheet for
the natural logarithm of the difference between the
in which k = 0.0224 minutes–1 and Δθ = 1 / 60 minute since temperatures of the contents of the calorimeter and of its
readings were taken at one second intervals. The temperature t surroundings (ln( t – tenv)).
versus time θ data set from Figure 4 is replotted in Figure 5
 Plot this function versus time (θ) and fit a linear
together with the corresponding corrected temperature profile
regression to the straight line region in the post-reaction
tc versus θ. The latter correctly remains constant in the post-
period and note the value of its slope k.
reaction period.
 Prepare a calculated column for the heat loss corrected
The procedure for obtaining the corrected temperature
temperature (tc = t + k Δθ sum( t – tenv)), plot this data set
profile involves the following steps:
versus time θ and read off the corrected temperature
 Pour a measured mass of the solvent into the calorimeter, values at the start and end of the reaction period (tc,i and
replace its lid and begin collecting contents temperature tc,f).
(t) and surroundings temperature measurements (tenv) at
Applied to the addition of 7.527 g of sodium hydroxide to
50.053 g of deionized water, this temperature correction

© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf

58 Chem. Educator, Vol. 21, 2016
procedure for heat loss raised the temperature change produced
by the dissolution process by 3.3% from 57.06 – 22.55 oC to
58.21 – 22.55 oC. The resulting reaction enthalpy change
ΔHreaction = – w Cp (tc,f – tc,i) = – w Cp (58.21 – 22.55)
= – 35.66 w Cp J
in which the combined heat capacity of the calorimeter and its
accessories (≈ 7 J oC–1) and its contents
w Cp = wcal Cpcal + wcon Cpcon ≈ 7 + wcon Cpcon J oC–1
Calorimeter and Contents Heat Capacity Determination.
The sodium hydroxide dissolution process proceeds from an
initial state of a suspension of sodium hydroxide solids (the
solute slt) in water (the solvent svt), for which the heat
capacity of the system is wslt Cpslt + wsvt Cpsvt, to a final state of
a solids-free aqueous sodium hydroxide solution (sln) for
which the heat capacity is wsln Cpsln = (wslt + wsvt) Cpsln. The
contents heat capacity may be assumed to be equal to the mean
of these two values, that is
wcon Cpcon = (wslt Cpslt + wsvt Cpsvt + (wslt + wsvt) Cpsln) / 2
= (7.527 Cpslt + 50.053 4.184 + 57.580 Cpsln) / 2
for the dissolution of 7.527 g of sodium hydroxide solids in
50.053 g of deionized water.
Reported specific heat (Cpsln) and density (ρsln) versus solute
molality (m) data for aqueous sodium hydroxide solutions at
20 oC [28] which are plotted in Figure 6 yield the following
relationships
Cpsln = 3.284 + 4543 exp[– ((m + 67.03) / 22.93)2)]: rmse
= 0.0178 J g–1 oC–1
ρsln = 0.9999 + 0.0426 m – 0.001304 m2 +1.787E+5 m3:
rmse 0.0005 g ml–1
in which the solution molality
m = nslt (mol) / wslv (g) / 1000(g kg–1)
= (wslt (g) / MWslt (g mol–1)) / (wslv (g) / 1000(g kg–1)) mol kg–1
The reason for the choice of molality, that is moles of solute
per kg of solvent, rather than the more familiar molarity, that is
moles of solute per liter of solution, as the measure of
concentration is subsequently discussed under the heading
“Molality versus Molarity.”. While a simple polynomial
regression was chosen to represent the relationship between
solution density and molality, the more versatile Gaussian
regression procedure was selected to handle the specific heat
versus molality relationship for reasons discussed in “The
Gaussian – A Versatile Regression Procedure”.
For the dissolution of 7.527 g of sodium hydroxide of molar
mass 40.00 g mol-1 in 50.05 g of water
© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf
John C. O’C. Young
m = (7.527 / 40.00) 1000 / 50.05 = 3.760 mol kg–1
corresponding to a specific heat value of
Cpsln = 3.284 + 4543 exp[– ((3.76 + 67.03) / 22.93)2)]
= 3.614 J g–1
and to a mean contents heat capacity of
wcon Cpcon = (7.527 0.706 + 50.053 4.184 + 57.580 3.614) / 2
= 211.4 J oC–1
and a calorimeter and accessories plus contents heat capacity
of
w Cp = wcal Cpcal + wcon Cpcon = 7 + 211.4 = 218 J oC–1
This heat capacity of the system is commonly assumed to be
equal to the heat capacity of the solvent, namely
w Cp = wslv Cpslv = 50.053 4.184 = 209.4 J oC–1
which is close to the computed value if the correction for the
heat capacity of the calorimeter and its accessories is added,
that is if
w Cp = wcal Cpcal + wslv Cpslv = 7 + 209.4 = 216 J oC–1
That the heat capacity of the solution differs little from that
of the solvent follows from the fact that addition of a moderate
amount of solute to a given volume of solvent has little effect
on its volume or on its heat storage capability, that is
wcon Cpcon = wslnCpsln = vsln ρsln Cpsln ≈ vslv ρslv Cpslv
from which since vsln ≈ vslv
Cpsln ≈ (ρslv / ρsln) Cpslv
indicating that addition of the solute to the solvent reduces its
specific heat value by approximately the same fractional
amount that it increases its density. Thus, at least at modest
concentration levels and providing that correction is made for
the heat capacity of the calorimeter and its accessories, the
simplifying assumption that the heat capacity of the solution is
equal to that of its solvent will be generally acceptable.
Reaction Enthalpy Change Determination. The enthalpy
change resulting from the dissolution reaction is equal to
minus the sum of its heat deliveries to the calorimeter, its
accessories and its contents, and through its walls to the
surroundings, that is
ΔHreaction = – w Cp (tc,f – tc,i) = – 218.4 (58.21 – 22.55) / 1000
= – 7.79 kJ
and its value per mole of solute
ΔHreaction / nslt = – 7.79 / (7.527 / 40.00) = – 41.4 kJ mol–1
Coffee Cup Calorimeter Heat Loss Correction Chem. Educator, Vol. 21, 2016 59

Figure 5. Heat loss corrected temperature profile.

Figure 6. Specific heat and density data for sodium hydroxide solutions.

Figure 7. Reaction enthalpy per mole of solute versus solution molality.

© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf

60 Chem. Educator, Vol. 21, 2016
at the molal concentration level of 3.760 mol kg–1. This and
values obtained at molal concentration levels of 1.01, 2.49,
5.00, 6.27, 7.47, 8.74 and 10.04 are listed in Table 1, plotted in
Figure 8 and yield a regression relationship of
ΔH / nslt = 0.0396 m2 + 0.465 m – 43.73 kJ mol–1: rmse = 0.14
The integral heat of solution of a solute in a solvent is
defined as its enthalpy of mixing per mole of solute and its
value is commonly reported at infinite dilution at a pressure of
100 kPa and a temperature of 25 oC. This relationship indicates
an integral heat of solution at infinite dilution, that is at m
equals zero, of – 43.73 kJ mol–1.
The purity of the sodium hydroxide reagent used in this
investigation was stated to be greater than 97% which may be
represented as 98.5 ± 1.5%. Reflecting this uncertainty, the
observed integral heat of solution at infinite dilution may be
expressed as
ΔH / nslt = – 43.73 / 0.985 = – 44.4 ± 0.7 kJ mol–1: rmse = 0.14
Ths magnitude of this range is indicative of uncertainty as to
the purity of the reagent rather than the indeterminate error of
the procedure which more realistically represented by the rmse
value.
Infinite dilution integral heat of solution data in water
reported by Murch and Giauque [29] for sodium hydroxide
having a water content represented by the mole ratio n = nH2O /
nNaOH yielded the following relationship:
ΔH / nslt = – 10,653 + 5,519 n + 10 cal mol–1 for n = 0 to 1
corresponding to a value of – 44.57 kJ mol–1 for n equals 0,
that is for an NaOH solute.
Molality versus Molarity
Experimental parameters such optical absorbance, pressure
and in the present instance temperature are commonly
measured to three figure accuracy, two certain and one
uncertain. When they are to be related to the concentration of
the activating substance, it is advantageous to prepare it to four
figure accuracy, so that indeterminate experimental errors may
be assumed to be related to the less sensitive parameter
measurement and accounted for, for example by a root mean
square error determination.
Solution masses (wsln in g) are more readily measured
accurately than their volumes (vsln in ml). Mass-based molality,
that is moles of solute per kilogram of solvent (m), is therefore
preferable to volume-based, temperature dependent molarity
measures of moles of solute (slt) per liter of solution (M).
However, the molarity measure of concentration is more
commonly reported and may be determined from the
corresponding molality value if the density (ρsln) of the
solution is known or separately determined. From the
relationships
M = wslt/MWslt / (vsln/1000): m
= wslt/MWslt / (wslv/1000): ρsln= wsln/vsln
it follows that
© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf
John C. O’C. Young
M / m = mass of solvent / volume of solution = wslv / vsln
= ρsln wslv / wsln = ρsln wslv / (wslv + wslt)
= ρsln / ( 1 + wslt / wslv) = ρsln / ( 1 + ( MWslt /1000) m)
from which the relationship between solution molarity and
molality is
M = ρsln / (1 / m + MWslt / 1000)
The Gaussian – A Versatile Regression Procedure
The Gaussian function is usually presented as f(x) = a exp[ –
(x – b)2 / 2c2 ] + d in which a, b, c and d are real constants.
When plotted against the independent variable x as abscissa, it
produces the familiar “normal” or “bell shaped” curve and the
half curve defines a useful sigmoid relationship.
In a slightly different form f(x) = A exp(– (x – B)2 / C2) + D,
a Gaussian function is included in the regression toolbox of the
Vernier Logger Pro 3.8.4 data collection and analysis program
[27] which also contains proportional, linear, quadratic, cubic,
quartic, quintic, power, natural exponent, natural logarithmic,
cosine squared and sine regression procedures together with a
useful custom relationship modification option.
In Figure 2, a cubic polynomial regression provided an
excellent fit to the density versus molality data set with a root
means square error value of only 0.000493 (0.036% at the
mid-range concentration level of 12.5 molal. For the
accompanying plot of specific heat on molality, a Gaussian
regression procedure was chosen which showed an rmse value
0.0169 (0.51% at the mid-range concentration level).
Reasons for this choice of a Gaussian regression procedure
are illustrated in Figure 9, in which the specific heat versus
molality data set is re-plotted and “fitted” with various
regression alternatives.
Another important advantage of Gaussian regression over
cubic and higher polynomial order regression procedures is
that it provides an explicit, non-iterative solution for the value
of the assumed error free independent variable (x)
corresponding to a given value of the assumed error prone
dependent variable (y).
For the Gaussian relationship
y = A exp[ – ((x – B) / C)2 ] + D,
this solution for the value of x is
x = B + C sqrt[ ln(A / (y – D)) ].
This inversion comes into play in experimental situations in
which a “standard curve” relationship is established between
the value of some physical parameter and a series of standard
solutions of known concentration of the causative substance,
and this relationship is then inverted to determine the
concentration corresponding to the observed value of this
physical parameter in one or more “unknown” solution(s).
Given that it is usually a simple matter to prepare the solute
concentrations in these standard solutions to at least three
figure accuracy, it is customary to treat the physical parameter
as the error prone dependent variable when establishing the
reliability of this relationship between it and concentration.
Coffee Cup Calorimeter Heat Loss Correction Chem. Educator, Vol. 21, 2016 61

Table 1. Reagent masses and thermal data

wslv wslt nslt m Cpslv Cpslt Cpsln w Cp ti.c tf,c H H/nslt
(g) (g) (mol) (mol/kg) (J g–1 oC–1) (J oC–1) (oC) (oC) (kJ) (kJ mol–1)
50.01 2.03 0.0508 1 .015 4.184 0.706 3.965 215.5 21.66 31.85 2.19 43.2
50.01 4.97 0.1243 2.486 4.184 0.706 3.744 216.4 22.62 46.92 5.26 42.3
50.05 7.53 0.1883 3.762 4.184 0.706 3.613 218.4 22.55 58.21 7.79 41.4
50.02 10.01 0.2503 5.004 4.184 0.706 3.521 220.9 23.45 69.42 10.15 40.6
50.05 12.55 0.3138 6.270 4.184 0.706 3.455 224.3 21.87 76.86 12.33 39.3
49.98 14.94 0.3735 7.473 4.184 0.706 3.409 227.2 23.94 86.32 14.17 37.9
50.04 17.50 0.4375 8.743 4.184 0.706 3.373 231.8 22.29 91.21 15.98 36.5
50.02 20.09 0.5023 10.041 4.184 0.706 3.347 236.1 22.58 97.52 17.69 35.2

Figure 8. Alternative regressional relationships.

Figure 9. Absorbance versus chromophore concentration profile.

Because the relationship between optical absorbance and
chromophore concentration commonly shows positive
deviation from Beer’s Law at low concentrations (d2Abs /
dConc2 > 0) and invariably exhibits negative deviation at high
concentrations (d2Abs / dConc2 < 0), the resulting sigmoid
profile is ideally suited to representation by a Gaussian
regression as is illustrated in Figure 9 for a ferrocene in ethanol
chromophore [30]. Inversion of the Gaussian regression
Abs = 2.292 – 2.496 exp[– (Conc + 6.026)2 / 19.842]: rmse
= 0.0196

© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf

62 Chem. Educator, Vol. 21, 2016
yields the relationship
Conc = – 6.026 + 19.84 sqrt[ ln[2.496 / (2.292 – Abs)]
= 10.07 ± 0.19 mM for Abs = 1.000 ± 0.0196
assuming the indicated indeterminate error range of ± 0.19 mM
at this middling range concentration level to be equal to that
corresponding to the rmse error in the absorbance reading. A
more detailed study of the use of the Gaussian regression
procedure to accommodate Beer’s Law deviations has been
reported previously [30].
It is noteworthy that CCD technology and linear diode array
detection in modern spectrophotometers extend their useful
absorbance range above 1, albeit with some decrease in
sensitivity (decreasing slope) at higher levels. Operation at
higher chromophore concentration levels usefully reduces
reagent consumption and disposal.
A final thought on the versatility of the Gaussian regression
procedure: when applied to the data set (0, 0), (1, 1), (2, 2),
(3, 3), (4, 4), (5, 5), it delivers a proportional relationship with
a root means square error value of 0.00000045.
References and Notes
1. Mahaffy, P. G.; Bucat, B.; Tasker, R.; Kotz, J. C.; Treichel, P. M.;
Weaver, G. C.; J. McMurry, J. Chemistry: Human Activity, Chemical
Reactivity; Nelson: Toronto, ON, 2011; p.212.
2. Radel, S.R.; Navidi, M. H. Chemistry, 2nd edn.; West: St. Paul, MN,
1994; p.250.
3. Hill, J.W.; Petrucci, R. H. General Chemistry: An Integrated
Approach, 2nd edn.; Prentice Hall: Upper Saddle River, NJ, 1999; p.
249.
4. Petrucci, R. H.; Harwood, W.S.; Herring, G.; Madura, J. D. General
Chemistry: Principles and Modern Applications, 9th edn.; Prentice
Hall: Upper Saddle River, NJ, 2007; p. 234.
5. Tro, N. J., Principles of Chemistry, A Molecular Approach, Prentice
Hall, New York, NY, 2010; p. 223.
6. Atkins, P.; Jones, L. Chemical Principles: The Quest for Insight, 2nd
edn.; Freeman: New York, NY, 2002; p. 292.
1. Brady, J.E.; Senese., F. Chemistry: Matter and Its Changes, 5th edn.;
Wiley, Hoboken, NJ, 2009; p. 225.
7. Moore, J.W.; Stanitski, C. L.; Jurs, P. C. Principles of Chemistry:
The Molecular Science; Brooks/Cole: Belmont, CA, 2010; p. 205.
© 2016 The Chemical Educator, S1430-4171(16)12683-6, Published 03/21/2016, 10.1333/s00897162683a, 21160053.pdf
View publication stats
John C. O’C. Young
8. http://lexington.k12.oh.us/hs/strickler/concrete/index.php/download_
file/view/280/85/ (accessed November 2, 2015).
9. Whitten, K. W.; Davis, R. E.; Peck, L. E.; Stanley, G. G. Chemistry,
9th edn.; Brooks / Cole: Belmont, CA, 2010; p. 553.
10. Stankus, J. J.; Caraway, J. D. J. Chem. Educ. 2011, 88, 1730–1731.
11. Postma, J. M.; Roberts, J. L.; Hollenberg, J. L. Chemistry in the
Laboratory, 7th edn.; Freeman, New York, NY, 2010; p. 14–3.
12. http://didomenico.lhseducators.com/ap_chem/chpt6-
thermo/calorimer_constant_lab.pdf (accessed November 2, 2015).
13. Greco, T. G.; Rickard, L. H.; Weiss, G. S. Experiments in General
Chemistry: Principles and Modern Applications; Prentice Hall,
Upper Saddle River, NJ, 2002; p. 97.
14. Nelson, J. H.; Kemp, K. C. Laboratory Experiments: Chemistry, The
Central Science, 8th edn.; Prentice Hall: Upper Saddle River, NJ,
2000, p. 301.
15. Totala, N. B.; Shimpi, M. V.; Shete, N. L.; Bhopate, V. S. Res.
Inventy: Int. J. Eng. Sci., 2013, 3(8), 27–31.
16. Citano, J. I. R. Thermochemistry: Calorimetry and Hess’s Law
17. http://chemistry.bd.psu.edu/jircitano/Calorimetry09.pdf (accessed
November 2, 2015).
18. http://jan.ucc.nau.edu/~jkn/152B-Calorimetry 6-09.htm (accessed
November 2, 2015).
19. http://www.chm.davidson.edu/vce/calorimetry/HeatofSolutionofSulf
uricAcid.html (accessed November 2, 2015).
20. https://www.dartmouth.edu/~chemlab/chem35/calor1/full_text/proce
dure.html (accessed November 2, 2015).
21. https://woodlawnschool.pbworks.com/f/Calorimetry+Read+Me.pdf
(accessed November 2, 2015).
22. http://chemlab.truman.edu/chemlab_backup/CHEM130Labs/Calorim
etry.htm (accessed May 24, 2015).
23. http:// www.chem.ualberta.ca/~ngee/Expt.G.html (accessed
November 2, 2015).
24. http://web.lemoyne.edu/giunta/chm151L/calorimetry.html (accessed
November 2, 2015).
25. http://web.williams.edu/wpetc/chemistry/epeacock/EPL_AP_GREY/
LABS/Calorimetry.pdf (accessed November 2, 2015).
26. http://chemlab.truman.edu/chemlab_backup/CHEM130Labs/Calorim
etry.htm (accessed November 2, 2015).
27. Vernier Software and Technology, Portland, Oregon 97225–2429.
28. Washburn, E. Intl. Critical Tables of Numerical Data, Phys., Chem.
and Tech.; McGraw-Hill, New York, NY, 1929; (a) v. III, p.79, (b) v.
V, p.115
29. Murch, L. E.; Giauque, W. F. J. Phys. Chem., 1962, 66, 2052–2059.
30. Young, J. C. O’C. Chem. Educator, 2015, 20, 1–8.