TEACHING NOTES for Investigation 5B TN35

INDIRECTLY DETERMINING AN ENTHALPY CHANGE

I n t e r n a t i o n a l
Syllabus relevance; Topic 5.2
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A calorimetry experiment for an enthalpy of reaction should be covered and the results evaluated.
Experiments could include Hess's Law labs.

Apparatus required
Per group
• Thermometer (preferably 0–50oC by 0.1oC intervals)
• Stop watch
• 100 cm3 measuring cylinder

B a c c a l a u re a t e
• Weighing bottle
• Polystyrene cup (at least 250 cm3 capacity)

General
Balance reading to 0.01 g

Chemicals required
• 2 mol dm-3 hydrochloric acid (~250 cm3 per group)
• Solid sodium hydrogencarbonate (bicarbonate) (~15 g per group)

C h e m i s t r y
• Solid anhydrous sodium carbonate (~10 g per group)

Notes
Probable timing – 60 minutes laboratory time

Sample data
Sodium hydrogencarbonate Sodium carbonate

I n v e s t i g a t i o n s
Initial mass 14.307 ± 0.0005 g   Initial mass 9.331 ± 0.0005 g  
Final mass 1.088 ± 0.0005 g   Final mass 1.104 ± 0.0005 g  

Sodium hydrogencarbonate Sodium carbonate

o o
Time (s) Temp ( C) Time (s) Temp ( C) Time (s) Temp (oC) Time (s) Temp (oC)
0 16.0 330 7.0 0 15.6 330 21.8
30 16.0 360 7.2 30 15.6 360 21.8
60 16.0 390 7.2 60 15.6 390 21.8
90 16.0 420 7.2 90 15.6 420 21.8
120 16.0 450 7.4 120 15.6 450 21.8
fo r

150 9.8 480 7.4 150 20.2 480 21.6

180 6.8 510 7.6 180 21.8 510 21.6
S t a n d a rd

210 6.6 540 7.6 210 22.0 540 21.6

240 6.6 570 7.6 240 22.0 570 21.6
270 6.8 600 7.8 270 22.0 600 21.4
300 7.0 630 7.8 300 22.0 630 21.4
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 TEACHING NOTES for Investigation 5B TN36
INDIRECTLY DETERMINING AN ENTHALPY CHANGE

I n t e r n a t i o n a l
Uncertainties: Time = ± 1 s Temp = ± 0.2 oC
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Volume of 2 mol dm-3 HCl for both = 100 ± 0.5 cm3

Relevant qualitative observations

In both cases there was very rapid effervescence as the white powder is added to the colourless solution, so much so
that it had to be added a little at a time over the first half minute to prevent the liquid frothing over the lip of the cup.
Eventually all of the powder dissolved to leave a clear colourless solution.

Data Analysis

B a c c a l a u re a t e
a)

Temperature change on the reaction of sodium

hydrogencarbonate with hydrochloric acid

18
Temperature /oC

16
14
12 9.7

C h e m i s t r y
10
8
6
4
0 100 200 300 400 500 600
Time /s

I n v e s t i g a t i o n s
Temperature change on the reaction of sodium carbonate
with hydrochloric acid

24
Temperature /oC

22

20
fo r
6.6
18
S t a n d a rd

16

14
0 100 200 300 400 500 600
Time /s
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Uncertainty in both values estimated as ± 0.1 oC

 TEACHING NOTES for Investigation 5B TN37
INDIRECTLY DETERMINING AN ENTHALPY CHANGE

I n t e r n a t i o n a l
b) Q = m . c . ∆T = 0.100 × 4.18 × 9.7 = 4.055 kJ
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(assuming density and specific heat capacity of 2 mol dm-3 HCl is the same as that of water)

14.307 − 1.088
n = = 0.1574 mol
84.01

4.055
∆H = = +25.77 kJ (positive sign as endothermic)
0.1574

B a c c a l a u re a t e
0.5 0.1
Uncertainties: m= ×100 = 0.50% T= ×100 = 1.03%
100 9.7

1.53
Uncertainty in ∆H = 0.50 + 1.03 = 1.53 % = 25.77 × = 0.395
100
Δ H = +25.8 ±0.4 kJ

c) Q = m . s . ∆T = 0.100 × 4.18 × 6.6 = 2.759 kJ

C h e m i s t r y
9.331 − 1.104
n = = 0.07762 mol
105.99

4.055
∆H = = -35.55 kJ (negative sign as exothermic)
0.1574

0.5 0.1

I n v e s t i g a t i o n s
Uncertainties: m= ×100 = 0.50% T= ×100 = 1.52%
100 6.6

2.02
Uncertainty in ∆H = 0.50 + 1.52 = 2.02 % = 35.55 × = 0.718
100
ΔH = -35.6 ± 0.7 kJ

d) NaHCO3 (s) + H+ (aq) ⇒ Na+ (aq) + H2O (l) + CO2 (g) ∆H = +25.77 kJ

Na2CO3 (s) + 2 H+ (aq) ⇒ 2 Na+ (aq) + H2O (l) + CO2 (g) ∆H = -35.55 kJ fo r

e) ∆H
2 NaHCO3 (s) ⇒ Na2CO3 (s) + H2O (l) + CO2 (g)
S t a n d a rd

∆H = 2 x +25.77 kJ mol-1 ∆H = -35.55 kJ mol-1

2 Na+ (aq) + H2O (l) + CO2

f) ∆H = (2 x +25.77) – (-35.55) = +87.09 kJ

Uncertainty = (2 x 0.395) + 0.718 = 1.508

Le v e l

ΔH = +87.1 ±1.5 kJ
 TEACHING NOTES for Investigation 5B TN38
INDIRECTLY DETERMINING AN ENTHALPY CHANGE

I n t e r n a t i o n a l
Evaluation
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(a) The value obtained is greater than the accepted value even taking into account the uncertainty. The experiment
has however yielded a most acceptable result as the agreement is within ~2½ % of the accepted value. The
estimated uncertainty of ~1.7% is also quite good. If the temperature changes had not been corrected for heat
losses the value obtained would have been +84.5 kJ. This suggests that the temperature correction has over-
compensated for the heat losses.

(b) In most thermochemistry determinations heat exchange with the surroundings is the major source of error
and in this case, because the reactions evolve a gas, it may be expected to be worse than in some other cases.
Heat exchange always leads to a smaller temperature change, irrespective of whether the reaction is exothermic

B a c c a l a u re a t e
or endothermic, and hence leads to smaller values for the enthalpy change being determined. In this case the
heat losses appear to be quite small, perhaps because the temperature changes are quite modest (<10 oC) and
the agreement without compensating for them is within about ½ % of the accepted value. Other sources of
systematic error would be ignoring the heat capacity of the polystyrene cup (which would also lead to a lower
temperature change and hence a lower value for ∆H), and the assumption that the density and the specific
heat capacity of the HCl are the same as those of water (internet sources give them as 1.04 g cm-3 and 4.04 J g-1
K-1 respectively. If these are correct the two deviations would conveniently just about cancel each other! With
regard to uncertainties the major contributor is the measurement of the temperature (± 0.2 oC, hence ± 0.4 oC
for ∆T, about 5 %, though a lower value was estimated for the extrapolated data on the graph). This is about 10
times greater than the uncertainty in the measurement of the volume of acid.

C h e m i s t r y
(c) The uncertainty could be significantly reduced by using a thermometer that reads to a greater precision. Many
electronic digital thermometers can be read to 2 dp, so reducing the uncertainty in the measurement of ∆T
to a similar order of magnitude to the measurement of the mass of HCl. This could itself be easily improved
by weighing the polystyrene cup before (hence giving a value for its heat capacity if compensating for this is
deemed worthwhile) and after adding the acid. In the absence of a better thermometer some improvement
could be made by using a greater mass of the solids along with a higher [HCl] to produce a greater temperature
rise, though greater heat exchange might soon offset any improvement. With regard to the assumptions made,
the density and the specific heat capacity of the acid used could have been measured as part of the investigation.
The method used to compensate for heat exchange seems to over-compensate pointing to the need to adopt a

I n v e s t i g a t i o n s
more sophisticated theoretical model. If the solids were finely powdered and the volume reduced so there was
little if any chance of the reagents bubbling over if it was all added at once, then perhaps the reaction could be
considered instantaneous.

(d) The reaction only occurs when the solid is heated. It is very difficult to make allowance for the contribution of
the enthalpy of reaction in the way the temperature changes as this is usually much less than the heat introduced
to raise the temperature to a level where the reaction would occur. Even then the reaction would be far from
instantaneous giving rise to problems compensating for temperature exchange with the surroundings which
would be very high at the temperatures required. The reverse reaction of solid sodium carbonate with water and
carbon dioxide should be spontaneous and exothermic at room temperature, but the amount of water would
have to be accurately controlled to prevent a solution occurring and again the reaction rate would be low, giving
problems with heat exchange and knowing when the reaction was complete.
fo r
S t a n d a rd
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