Calorimetry

Franz Laurence L. Alvarez

Louise Gabrielle M. Valdez
Theoretical Framework
 Calorimetry
 Science of measuring the heats of reaction
 Calorimetric techniques: based on the measurement of
heat that may be:
 Generated (exothermic)
 Consumed (endothermic)
 Dissipated
 In measuring change in enthalpy (∆H):
 Construct a “surroundings”  retains heat, where temperature
change is observed
Theoretical Framework
 Calorimeter
 Apparatus used to measure heat released or absorbed
 Acts as the “surroundings”
 Changes temperature when heat is transferred to or from the
system
Calorimeter:
Theoretical Framework
 Heat capacity
 Quantity of heat required to change an object’s
temperature by 1K
 Specific heat capacity
 Quantity of heat required to change the temperature of
1 gram of a substance by 1K
Theoretical Framework
 The heat released (Q) by a reaction is absorbed by
the calorimeter and any substances in the
calorimeter.
 The following energy balance exists if the only
substance in the calorimeter is water:
 0 = Qcal + Qwater
 Remember: First law of Thermodynamics 
when energy is transferred from one object to
another, it appears as work and/or as heat
Experimental
 Part A: Calorimeter Constant
10mL of tap Calorimeter with Record temperature This is the initial
water thermometer until 3 identical temperature of
calorimeter and
readings water.

10mL of hot Heat to 50oC 50mL of tap

(use another
water water
thermometer)

Calorimeter with Record temperature

tap water every 3s until temp This is the final
/equilibrium
becomes constant for 4 temperature.
successive readings.
 Part B: Heat of Fusion
10mL of tap Calorimeter with Record This is the initial
water thermometer temperature until temperature of
calorimeter and
3 identical water.
readings

Determine weight of
beaker with tissue and
weight of ice.
Weigh 10g of ice
Calorimeter in beaker with
with tap water tissue paper at
bottom

Record temperature
every 3s until temp This is the
becomes constant for 4 final
successive readings. /equilibrium
temperature.
 Part C: Heat of Reaction
Record temperature of Read temperature
Measure
each reagent (initial temp)
Place in water bath if
volume
temp is not equal

Set I:
Record temperature every Mix reagents in
5.5mL 6M HCl + 4.5mL 6M
NaOH 3s until temp becomes calorimeter
constant
Set II
5.5mL 6M HOAc + 4.5mL
6M NaOH

Set III
5.5mL 6M HCl + 4.5mL 6M
NH4OH
Results
 Part A
Time (s)
0 3 6 9 12 15
Temperature (oC)
40 41 41 41 41 41
 Mass of tap water: 10g
 Mass of hot water: 10g
 Initial temperature of tap water: 35oC
 Initial temperature of hot water: 50oC
 Equilibrium temperature: 41oC
 Calorimeter constant, cal/oC: 5 cal/oC
Part A.
Evaluation of Calorimeter Constant

41.2

41
Temperature (C)

40.8

40.6

40.4

40.2

40

39.8
0 2 4 6 8 10 12 14 16
Time (s)
Results
 Part B
Time (s) Temp (oC) Time (s) Temp (oC)

 Mass of tap water: 10g 0 23 33 8.5

3 20 39 8
 Mass of ice + beaker + tissue: 6 17 42 8
34.45g 9 15 45 7.5
 Mass of beaker + tissue: 24.39g 12 13 48 7.5
 Mass of ice: 10.06g 15 12 51 7

 Initial temperature of tap water: 18 11 54 7

34oC 21 10 55 7
24 10 57 7
 Initial temperature of ice: 0oC 27 9
 Equilibrium temperature: 7oC 30 9
 Calorimeter constant: 5 cal/oC
 Heat of fusion of ice, cal/g: 37.74
cal/g
Part B.
Evaluation of Heat Fusion of Ice

25

20
Temperature (C)

15

10

0
0 10 20 30 40 50 60
Time (s)
Results
 Part C.
 Set I: 5.5mL 6M HCl + Time (s) Temperature (oC)
4.5mL 6M NaOH 0 35
3 45
6 54
 Mols of HCl: 0.033 mols 9 58
12 60
 Mols of NaOH: 0.027 mols 15 62
 Mols of limiting reagent: 18 63

0.027 mols 21 63
24 63
 ∆H of neutralization: 27 63

-15.56 x 103 cal/mol

Part C: Set I
Evaluation of Heat of Reaction of Set I

70
60
Temperature (C)

50
40
30
20

10
0
0 5 10 15 20 25 30
Time (s)
 Part C.
 Set II: 5.5mL 6M HOAc + Time (s) Temperature (oC)
4.5mL 6M NaOH 0 50
3 55
 Mols of HOAc: 0.033 mols 6 56
9 56.5
 Mols of NaOH: 0.027 mols
12 56.5
 Mols of limiting reagent:
15 56.5
0.027 mols
 ∆H of neutralization:
-3.61 x 103 cal/mol
Part C: Set II
Evaluation of Heat of Reaction of Set II

57
56
55
Temperature (C)

54
53
52
51
50
49
0 2 4 6 8 10 12 14 16
Time (s)
 Time (s) Temperature (oC)
 Part C.
0 34
 Set III: 5.5mL 6M HCl + 3 43
4.5mL 6M NH4OH 6 49
9 52
 Mols of HCl: 0.033 mols 12 55
15 56
 Mols of NH4OH:
18 57
0.027 mols
21 57.5
 Mols of limiting reagent: 24 58
0.027 mols 27 58
 ∆H of neutralization: 30 58
-13.33 x 103 cal/mol
 Evaluation of Heat of Reaction of Set III

70
60
Temperature (C)

50
40
30
20

10
0
0 5 10 15 20 25 30 35
Time (s)
Discussion
 Part A: Calorimeter Constant
 Qhot water + Qtap water + Qcalorimeter = 0
 *Q = m c ∆ t ; Qcalorimeter = ccalorimeter ∆ t
 Qcal = -mtapc∆ttap – mhotc∆thot
Part A: Calculations

 Qcal = -mtapc∆ttap – mhotc∆thot

= -(10g) (1.00 cal/goC) [(41-35) + (41-50)]oC
= 30 cal

 Ccal = Qcal/∆t
= 30cal / (41-35)oC = 5 cal/oC
Discussion

 Part B: Heat of Fusion

 ∆Hfusion = (-Qice – Qtap – Qcal) ÷ mice

Part B: Calculations

 ∆Hfusion = -Qice – Qtap – Qcal ÷ mice

= {[-10.06g(4.184J/goC)(7-0)oC] – [10g(4.184J/goC)
(7-34)oC] –
[(5cal/oC)(7-34)oC(4.184J/cal)]} ÷ 10.06g

= 139.15 J/g  33.25 cal/g

Discussion
 Part C: Heat of Neutralization

 ∆Hneut = (-Qcal – Qsol’n) ÷ mollimiting

 ∆ Hneut = (-Ccal∆t – msol’ncsp∆t) ÷ mollimiting
 ∆ Hneut = [-msol’ncsp(tf - ti) – Ccal (tf - ti)] ÷ mollimiting
Part C: Set I: Calculations

 ∆Hneut = (-Qcal – Qsol’n) ÷ mollimiting

 ∆ Hneut = (-Ccal∆t – msol’ncsp∆t) ÷ mollimiting
 ∆ Hneut = [-msol’ncsp(tf - ti) – Ccal (tf - ti)] ÷ mollimiting

= [(-10g)(1.00cal/goC)(63-35)oC –
(5cal/ oC)(63-35)oC] ÷ 0.027 mol
= -15.56 x 103 cal/mol
Part C: Set II: Calculations

 ∆Hneut = (-10g)(1.00cal/goC)(56.5-50)oC –
(5cal/oC)(56.5-50)oC ÷ 0.027 mol

= -3.61 x 103 cal/mol

Part C: Set III: Calculations

 ∆Hneut = (-10g)(1.00cal/goC)(58-34)oC –
(5cal/oC)(58-34)oC ÷ 0.027 mol

= -13.33 x 103 cal/mol

 COMPARISON OF VALUES
 Experimental Values  Theoretical Values
 ∆Hfusion = 139.15 J/g  333.55 J/g
 ∆Hneut(SET I) = -15.56 x 103  -13.48 x 103 cal/mol
cal/mol
 ∆Hneut(SET II) = -3.61 x 103  -13.42 x 103 cal/mol
cal/mol
 ∆Hneut(SET III) = -13.33 x 103  -11.92 x 103 cal/mol
cal/mol
Conclusion and Recommendation
 Calorimetry is very helpful in determining heats
of reaction especially in chemistry experiments.
We found out that heat is related with temperature
and it can be defined in many ways.
 Conservation of energy is also a part of heat
processes were heat is neither created or
destroyed but instead, it is passed on by the
system to the surroundings or vice versa.
Conservation of such energy gives definition for
endothermic and exothermic reactions.
Conclusion and Recommendation
 Calorimeter constant is the specific heat of the
calorimeter. Specific heats of different calorimeters vary
from each other.
 The heat of fusion is the amount of thermal energy which
must be absorbed or evolved for 1 mole of a substance to
change states from a solid to a liquid or vice versa. The
heat of fusion in the experiment may be positive or
negative with respect to different substances. It is
endothermic in the experiment with respect to ice.
Conclusion and Recommendation

 The heat of neutralization is the amount of heat

involved (either given off or absorbed) in the
neutralization reaction of acids and bases to form
salt and water.

 Different factors affect the experiment that led to

different experimental errors and that not all
experimental measurements were so accurate.