CALORIMETR

Y
Denielle B. Baybay
Charmaine Joy A. Cabaña
 Theoretical Framework
w !
 Calorimetry
k no
o
• the science of measuring heat changes
t
e d
in physical and chemical processes
e n o th e
a involve
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u n
• essential since all reactions
changes in energy j e t t
c orb
o ed !

t y o m o e b s
o abm.
n eat iu
r
h a f ers f o
r d = ui
s e eq
H l ib

W e a t
H l th H
a
ans eleiev
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e
r at ar ch
n t i
u
How to measure change in
Enthalpy (∆H)?
• By constructing a “surrounding” which
retains heat (so temperature may be
observable)

CALORIMETER
is the answer!!!
Calorimeter as “the surrounding”!
Definition of Terms
• Specific heat capacity (s)
• intensive property
• Amount of heat required to raise the temperature of
one gram of a substance by one degree Celcius.
• Heat capacity (C)
• extensive property
• amount of heat required to raise the temperature of a
given quantity of the substance by one degree
Celcius.
Experimental
• Part A: Calorimeter Constant
10mL of tap Calorimeter with Record This is the initial
water thermometer temperature until temperature of
calorimeter and
3 identical water.
readings

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
becomes constant for /equilibrium
4 successive temperature.
readings.
Results
• Part A:
Time (sec) 0s 3s 6s 9s 12s 15s
Temperature 39 39 40 40 40 40
(°C)

Mass of tap water 4.08g

Mass of hot water 10.57g
Initial temperature of tap water 29°C
Initial temperature of hot water 50°C
Equilibrium Temperature 40°C
Calorimeter Constant 5.53 cal°C
Plot of Temperature vs. Time
40.2
40
39.8
Temperature (C)

39.6
39.4
39.2
39
38.8
38.6
38.4
0 3 6 9 12 15
Part A: Calorimeter Constant
• Used to calculate amount of heat required to
raise contents of calorimeter by change in
temperature. (Ccal = qcal/∆T)
• qtotal = 0
• qhot water + qtap water + qcalorimeter = 0
• *q = m s ∆ T; qcal = -qhot - qtap
• qcal = -mtaps∆Ttap – mhots∆Thot

And
Remember
Heatintransfers from
an isolated one object
system,
this?
to another
heat gained by one
until is
thing they achieve
equal to theEQUILIBRIUM.
lost of another.
 o C;
1 c al/ g
ere s : w a ter )
wh ea to f
Part A: Calculations fi c h
(speci

• qcal = -mtaps∆Ttap – mhots∆Thot

= -[(4.08g) (1.00 cal/goC) (40-29)oC] – [(10.57g)
((1.00 cal/goC) (40-50) oC]
= 60.82 cal
• Ccal = qcal/∆T
= 60.82cal / (40-29)oC = 5.53 cal/oC
Experimental
• Part B: Heat of Fusion

10mL of tap Calorimeter Record This is the

water with temperature initial
temperature of
thermometer until 3 identical calorimeter and
readings water.

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

Record temperature
every 3s until temp This is the final
becomes constant for /equilibrium
4 successive readings. temperature.
Results
• Part B:
Time (s) Temp() Time (s) Temp(oC)
0 17 24 5
3 15 27 4
6 13 30 4
9 11 33 3.35
12 11 36 3.9
15 11 39 3.9
18 5 42 3.9
21 5 45 3.9
Mass of tap water 4.08g
Mass of ice + beaker + tissue 38.27g
Mass of beaker + tissue 28.65g
Mass of ice 9.62g
Initial temperature of tap water 27
Initial temperature of ice 0
Equilibrium temperature 3.9
Calorimeter constant 5.53 cal/°C
Heat of fusion of ice 138.90 J/g
 18
16
14
Temperature (C)

12
10
8
6
4
2
0
0 3 6 9 12 15 18 21 24 27 30 33 36 39 42 45

Time (s)
Part B: Heat of Fusion of Ice
• (a.k.a. enthalpy of fusion or specific melting heat) energy
required to change one mole of a substance from ice(solid) to
water(liquid) at its melting point (0 °C)
The following relationships will be used in part B of the
experiment:
A. Heat lost by water in the calorimeter = original mass of water
in the calorimeter x specific heat of the water x change in
temperature of the water
q = m s ∆T
B. heat given off by the water = heat absorbed by the ice

C. heat absorbed by the ice = heat of fusion of ice x

mass of melted ice
q = ∆Hfusion x Mice
 s ∆ T
Part B: Calculations q =m o C;
1 84J / g
s : 4 . te r)
e r e w a
• ∆Hfusion = qfusion ÷ mice wh
p e ci fic h e a t of
(s
• qcal + qtap + qice +qfusion= 0
• ∆Hfusion = (-qice – qtap – qcal) ÷ mice
i

= {[-9.62g(4.184J/goC)(3.9-0)oC] – [4.08g(4.184J/goC)(3.9-
29)oC] – [(10.14cal/oC)(3.9-29)oC(4.184J/goC)]} ÷ 9.62g
= 138.90 J/g or 33.20 cal/g
Heat of Reaction
• heat liberated or absorbed when a chemical reaction
takes place

• Heat (or enthalpy) of neutralization (∆H)

• heat evolved when an acid and a base react to form a
salt plus water
• Heat measurements -> performed by carrying out the
reaction in a calorimeter
• Heat (Q) given off by the neutralization reaction
• absorbed by the reaction solution and the
calorimeter.
• Both the solution and calorimeter increase in
temperature due to the absorbed heat
• increase - can be measured with a
thermometer.
• ∆H is negative – heat is evolved
positive if heat is absorbed.
Part C. Heat of Reaction
Set I
5.5 ml 6M HCl + 4.5 ml 6M NaOH

Set II
5.5 ml 6M HOAc+ 4.5 ml 6M NaOH

Set III
5.5 ml 6M HCl + 4.5 ml 6M NH4OH
 Record If temperatures are Record as initial
temperature of not equal, place in temperature
each reagent water bath

Take Mix all reagents Measure

temperature in the volume of all
readings every calorimeter solutions using
3 seconds until a syringe
a constant
temperature is
obtained.
Results for Set I (Part C)
 Time (s) Temperature (oC)
0 40
3 42
6 43
9 43
12 43
15 43.5
18 43.5
21 43.5
24 43.8
27 43.8
• Mols of HCl: 0.033 mols 30 43.8
• Mols of NaOH: 0.027 mols 33 43.8
• Mols of limiting reagent: 0.027 mols
• ∆H of neutralization: - 1.980 x 103 cal/mol
Calculations:
• 5.5 ml 6M HCl
• 4.5 ml 6M NaOH

• HCl(aq) + NaOH  H2O(l) + NaCl(s)

To find the concentration of the acid in the solution,

M1V1 = M2V2 3.3M
M1 = M2V2 0.01L
V1 = 0.033 mol/L
M1 = (6M)(5.5ML)
10ML
M1 = 3.3M
To find the concentration of the base in the solution,
M1V1 = M2V2 3.3M
M1 = M2V2 0.01L
V1 = 0.027 mol/L
M1 = (6M)(4.5ML)
10ML
M1 = 2.7M

*by merely inspecting the concentration of the acid and the

base in the solution, it can be deduced that the BASE is the
LIMITING REAGENT.
To find the heat of neutralization,
• ∆Hneut = -Qcal – Qsol’n÷ mollimiting
• ∆Hneut = (-Ccal∆t - msol’ncsp∆t) ÷ mollimiting
• ∆Hneut = [-msol’ncsp(tf-ti) – Ccal(tf-ti)] ÷ mollimiting

Substitung the values,

∆Hneut = [(-10g)(1.00cal/goC)(43.8-40oC) -
(4.07cal/oC)(43.8-40)oC] ÷ 0.027 mol
∆Hneut = - 1.980 x 103 cal/mol
Results for Set II (Part C)
 Time (s) Temperature (oC)
0 60
3 82
6 82
9 82
12 82

• Mols of HOAc: 0.033 mols

• Mols of NaOH: 0.027 mols
• Mols of limiting reagent: 0.027 mols
• ∆H of neutralization: -1.146 x 104 cal/mol
Calculations:
• 5.5 ml 6M HOAc
• 4.5 ml 6M NaOH

• HOAc + NaOH  NaOAc + H2O

To find the concentration of the acid in the solution,

M1V1 = M2V2 3.3M
M1 = M2V2 0.01L
V1 = 0.033 mol/L
M1 = (6M)(5.5ML)
10ML
M1 = 3.3M
To find the concentration of the base in the solution,
M1V1 = M2V2 3.3M
M1 = M2V2 0.01L
V1 = 0.027 mol/L
M1 = (6M)(4.5ML)
10ML
M1 = 2.7M

*by merely inspecting the concentration of the acid and the

base in the solution, it can be deduced that the BASE is the
LIMITING REAGENT.
To find the heat of neutralization,
• ∆Hneut = -Qcal – Qsol’n÷ mollimiting
• ∆Hneut = (-Ccal∆t - msol’ncsp∆t) ÷ mollimiting
• ∆Hneut = [-msol’ncsp(tf-ti) – Ccal(tf-ti)] ÷ mollimiting

Substitung the values,

∆Hneut = [(-10g)(1.00cal/goC)(82-60oC) -
(4.07cal/oC)(82-60)oC] ÷ 0.027 mol
∆Hneut = -1.146 x 104 cal/mol
Results for Set III (Part C)
 Time (s) Temperature (oC)
0 30
3 30
6 37
9 36
12 36
15 36
18 36

• Mols of HOAc: 0.033 mols

• Mols of NaOH: 0.027 mols
• Mols of limiting reagent: 0.027 mols
• ∆H of neutralization: -3.13 x 103 cal/mol
Calculations:
• 5.5 ml 6M HCl
• 4.5 ml 6M NH4OH

• NH4OH + HCl NH4Cl + H2O

To find the concentration of the acid in the solution,
M1 V 1 = M 2 V 2 3.3M
M1 = M2 V 2 0.01L
V1 = 0.033 mol/L
M1 = (6M)(5.5ML)
10ML
M1 = 3.3M
To find the heat of neutralization,
• ∆Hneut = -Qcal – Qsol’n÷ mollimiting
• ∆Hneut = (-Ccal∆t - msol’ncsp∆t) ÷ mollimiting
• ∆Hneut = [-msol’ncsp(tf-ti) – Ccal(tf-ti)] ÷ mollimiting

Substitung the values,

∆Hneut = [(-10g)(1.00cal/goC)(36-30oC) -
(4.07cal/oC)(36-30)oC] ÷ 0.027 mol
∆Hneut = -3.13 x 103 cal/mol
Comparison of values
Experimental Values Theoretical Values
• ∆Hfusion = 138.90 J/g • 333.55 J/g
• ∆Hneut(SET I) = - 1.980 x 103 • -13.48 x 103 cal/mol
cal/mol
• ∆Hneut(SET II) = - -1.146 x 104 • -13.42 x 103 cal/mol
cal/mol
• ∆Hneut(SET III) = -3.13 x 103 • -11.92 x 103 cal/mol
cal/mol
Conclusions and Recommendations
• Calorimetry is helpful in determining heats of reaction in
chemistry experiments. Heat is related with temperature
and can moreover be defined in many ways
• Calorimeter constant – specific heat of the calorimeter.
Specific heats of different calorimeters vary from each
other.
• Heat of Fusion – amount of thermal energy which must
be absorbed or evolved for 1 mole of a substance to
change state
- may be positive or negative with respect to
the substance
Conclusions and Recommendations
• Heat of neutralization – amount of heat involved (either
given off or absorbed) in the neutralization reaction of
acids and bases to form salt and water
• To minimize error, implementation of proper use of the
apparatus for the calorimetry setups are recommended
• Other unavoidable sources of error served to cause a
large percent error for each part of the experiment.
However, the techniques associated with calorimetry
were practiced, providing valuable experience.