Thermochemistry

A. Objectives
1. Determine the heat change through a simple experiment
2. Determine the calorimeter constant
3. Determine the change of entalphy reaction
B. Theory

A calorimeter is an object used for calorimetry, or the process of measuring the

heat of chemical reactions or physical changes as well as heat capacity. Differential
scanning calorimeters, isothermal microcalorimeters, titration calorimeters and
accelerated rate calorimeters are among the most common types. A simple calorimeter
just consists of a thermometer attached to a metal container full of water suspended
above a combustion chamber.

Heat is energy transferred from one object to object because the difference
temperature . In the seventeenth century, Galileo, Newton, and other scientists
generally support the theory of ancient Greek atomic experts, who consider that heat
as a form of molecular motion. In the next century, methods were developed to
measure the amount of heat that is leaving or entering into an object quantitatively,
and found that when two objects equal to the amount of heat that enters another object.
This discovery led to the development of the theory of heat seemed to work as an
eternal material -an invisible fluid called "caloric" - which is not created and
destroyed, but only flows out of objects to other objects (Tipler, 1998).
A calorimeter measures the heat evolved or absorbed by a system in a chemical
change, e.g. a chemical reaction. The heat evolved (or absorbed) by a chemical
reaction causes the temperature of the calorimeter to rise (or fall). The magnitude of
the temperature rise (or fall) depends on the quantity of heat evolved (or absorbed) in
the reaction and on the knowledge of the heat capacity of the calorimeter. The latter is
defined as the quantity of heat absorbed by the calorimeter necessary to raise the
temperature of the calorimeter by exactly one K, hence it is always positive. The heat
capacity CS of the calorimetric system is calculated as:
heat absorbed by the calorimeter
CS =
temperature rise produced
(http://www.chemistry.mcmaster.ca/~ayers/chem2PA3/labs/CALORIMETRYI
NTRO.pdf)
 To find the enthalpy change per mole of a substance A in a reaction between two
substances A and B, the substances are added to a calorimeter and the initial and
final temperatures (before the reaction started and after it has finished) are noted.
Multiplying the temperature change by the mass and specific heat capacities of the
substances gives a value for the energy given off or absorbed during the reaction.
Dividing the energy change by how many moles of A were present gives its enthalpy
change of reaction. This method is used primarily in academic teaching as it describes
the theory of calorimetry. It does not account for the heat loss through the container or
the heat capacity of the thermometer and container itself.
(http://en.wikipedia.org/wiki/Calorimeter

Endothermic and Exothermic Reactions

Most reactions of interest to chemists are carried out at constant pressure,
chemists generally use H rather than U as a measure of the change in
energy of the system. However, one can be calculated from a measurement of the
other. Imagine that a reaction involving a stoichiometric mixture of reactants ( the
system ) is carried out in a constant pressure reaction vessel with diathermal walls
immersed in a water bath (the surroundings). If the temperature of the water bath
increases, heat flows from the system (the contents of the reaction vessel) to the
surroundings (the water bath and the vessel). In this case, we say that the reaction is
exothermic(chemical reactions that are accompanied by the release of heat). If the
temperature of the water bath decreases, the heat flows instead from the surroundings
to the system, and we say that the reaction is endothermic(chemical reactions that are
accompanied by the absorption of heat).(Thomas Engel, Philip Reid, 2010: 64)

Calorimetry and heat Capacity

The amount of heat transferred during a reaction can be measured with a device
called calorimeter, at its simplest, a calorimeter is just an insulated vessel with stirrer,
a thermometer, and loose-fitting lid to keep the contents at atmospheric pressure. The
reaction is carried out inside the vessel, and the heat evolved or absorbed is calculated
from the temperature change. Because the pressure inside the calorimeter is constant
(atmospheric pressure), the temperature measurement makes it possible to calculate
the entalphy change H during a reaction.
A somewhat more complicated device called a bomb calorimeter is used to
measure the heat released during a combustion reaction, or burning of a flammable
substance. The sample is placed in a small cup and sealed under an oxygen
 atmosphere inside a steel bomb that is placed in an insulated, water-filled container.
The reactants are ignited electrically, and the evolved heat is calculated from the
temperature change of surrounding water. Since the reactionn takes place at constant
volume but not constant pressure, the measurement provides a value for E rather than
H. (McMurry-Fay.2008.285-285)

C. Apparatus and reagent

Apparatus : Reagent :
Calorimeter NH4OH 1 M
Beaker glass CH3OOH 1 M
Thermometer CuSO4 0,5 M
HCl 1 M Hot and cold water
NaOH 1 M

D. Procedure
1. Determination of calorimeter constant

Put 20mL cold water into stir the mixture and record the
calorimeter, record the temperature temperature for 10minutes at
Take 20 mL hot water, record the interval 1 minutes after mixing
temperature add into the calorimeter

Create a graph of temperature vs time

interval
Determinethe Calorimeter Constant

2. Determination of neutralization heat of acid-base

Put 20mL acid into calorimeter,

mix and record the
record the temperature
temperature for 5 minutes
Put 20 mL base into beaker glass,
with interval 0,5 minutes
record the temperature, add into the
calorimeter
1. Mix NaOH- HCl for the
first experiment
2. Mix NaOH CH3COOH
for the second experiment
3. Mix HCl NH4OH for the Create a graph of temperature vs
time interval
third experiment Calculate the of neutralization heat
of acid-base reaction
 3. Determination of heat dilution of ethanol in water

Put water and ethanol make it mix and record the

volume of mixture 10 ml record the temperature for 4 minutes
temperature initial of water and with interval 0,5 minutes
ethanol (2:8; 4:6; 6:4; 8:2)

E. Observation sheet
a. Determination of calorimeter constant Calculate the dilution heat of
Temperature of cold water in calorimeter = 29 Cethanol
= 302 K
in water
Temperature of hot water before being put into a calorimeter = 58C = 331 K
Temperature final = 34 C = 307 C
Water temperature after mixing for 10 minutes at intervals of 1 minute

t (min) 1 2 3 4 5 6 7 8 9 10
T (C) 35 34 34 34 34 34 34 34 34 34

b. Determination of neutralization heat of acid-base reaction

Temperature of HCl = 30C Temperature of CH3COOH = 30C
Temperature of NaOH = 30C Temperature of NH4OH = 29C
Temperature after mixing = 35
Time intervals
0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0 4,5 5,0
(minute)
Temperature
NaOH HCl 34, 34, 34, 34, 34, 34, 34, 34, 34,
35
5 5 5 5 5 5 5 1 1
NaOH
34 34 34 34 34 34 34 34 34 34
CH3COOH
HCl NH4OH 34 34 34 34 34 34 34 34 34 34

c. Determination of heat dilution of ethanol in water

Temperature of water = 30 C = 303 K
Temperature of ethanol = 29 C = 302 K
Mix water and ethanol with composition a follows :
Composition A B C D

Volume of water (mL) 2 4 6 8

Volume of ethanol (mL) 8 6 4 2

Temperature after mixing :

Time intervals 0,5 1,0 1,5 2,0 2,5 3,0 3,5 4,0
Temperature Composition A 31, 31, 31, 31, 31, 31,
31 31
(C) 2 2 2 2 2 2
Composition B 32 32 32 32 32 32 32 32
Composition C 32, 32,
32 32 32 32 32 32
2 2
Composition D 31, 31, 31,
31 31 31 31 31
5 5 5
E. Analysis Data
1. Determination of calorimeter constant

35.2

35

34.8

34.6

34.4
Temperature 34.2
Hot water and Cold Water
34

33.8

33.6

33.4
1 2 3 4 5 6 7 8 9 10

Time interval

Graph 1. Temperature vs time interval of cold and hot water

water = 1g/mL
C water = 4,2 j/g K
Temperature of cold water in calorimeter = 29 C = 302 K
Tempperature of hot water before being put into a calorimeter = 58C = 331 K
Temperature final = 34 C = 307 C
m cold water= x v
g
1 x 20 mL
mL
20 g
mh ot water = x v
g
1 x 20 mL
mL
20 g
Q1=m c T
0
307302 K
1 1
20 gr 4,2 J g K
420 J
Q2=m c T
 0
331307 K
1 1
20 gr 4,2 J g K
2016 J

Q3=Q2Q1 =2016 J 420 J =1596 J

0
307302 K


Q3 1596 J
C= =
T
2. Determination of neutralizatiom heat of acid base
HCl NaOH

NaOH - HCl
35.2
35
34.8
34.6
34.4 NaOH - HCl
Temperature
34.2
34
33.8
33.6
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Time Interval

HCl+ NaOH NaCl+ H 2 O

0,02mol 0,02mol
0,02mol 0,02mol 0,02mol 0,02mol
- - 0,02mol 0,02mol

Tconstant = 34,5 0C = 307,5 0K , Tinitial= 300C = 3030K

mol NaCl=1 M 20 ml=20 mmol=0,02 mol
Volume of the solution is 40 ml, so the mass of the solution
mass=40 ml 1,03 gr ml1=41,2 gr
Q4 =m c T
 0
307,5303 K
1 1
41,2 gr 3,96 J g K
734,184 J
Q5=C T
0
307,5303 K
1
319,2 J K
1437,75 J
Q6=Q 4+ Q5=2171,934 J
Q6
H= =108596,7 J mol1 =108,6 KJ 1
0,02 mol

NaOH CH3COOH

NaOH - CH3COOH
40
35
30
25
20 NaOH - CH3COOH
Temperature
15
10
5
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Time Interval

NaOH +C H 3 COOH C H 3 COONa+ H 2 O

0,02mol 0,02
0,02mol 0,02mol 0,02mol 0,02mol
- 0,02mol 0,02mol

Tconstant = 340C = 3070K, Tinitial = 300C = 3030K

mol CH3COONa 1 M 20 ml=20 mmol=0,02 mol
Volume of the solution is 40ml, so the mass of the solution
mass=40 ml 1,098 gr ml1=43,92 gr
Q4 =m c T
 0
307303 K
1 1
43,92 gr 4,02 J g K
706,2336 J
Q5=C T
0
307302 K
1
319,2 J K
1276,8 J
Q6=Q 4+ Q5=1983,0336 J
Q6
H= =99151,68 J mol1=99,2 KJ mol1
0,02 mol

HCl NH4OH

HCl - NH4OH
40
35
30
25
20 HCl - NH4OH
Temperature
15
10
5
0
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5

Time Interval

H Cl + N H 4 OH N H 4 Cl+ H 2 O
0,02mol 0,02mol
0,02 mol 0,02 mol 0,02 mol 0,02 mol
- - 0,02 mol 0,02 mol

Tconstant= 340C= 3070K, Tinitial= 290C = 301,250K

mol NH4Cl 1 M 20 ml=20 mmol=0,02 mol
Volume of the solution is 40ml, so the mass of the solution
mass=40 ml 1,015 gr ml1=40,6 gr
Q4 =m c T
 0
307301,25 K
1 1
40,6 gr 3,96 J g K
732,492 J
Q5=C T
0
307301,25 K
1
258,46 J K
1436,4 J
Q6=Q 4+ Q5=2159,892 J
Q6
H= =107994,6 J mol1
0,02 mol
3. Determination of heat dilution of ethanol in water

Composition A
Tconstant = 31,2 oC = 304,2 K
Mass of wate r = . V = 1 g/ml. 2 ml = 2 gram
T water = 30 C = 303 K
q1 = mw.c.T
= 2 g. 4,2 J/g 0K. (304,2 - 303) 0K = 10,08 J
Mass of ethanol = . V = 0,793 g/ml. 8 ml = 6,344 g
Mole of ethanol = m/Mr = 6,344 g/ 46 g/mole = 0,138 mole
Tethanol = 29 oC = 302 0K
q2 = me.c.T
= 6,344 g. 2,4 J/g 0K. (304,2 - 302) 0K = 33,496 J
q3 = C. T
= 319,2 J/0K . (304,2 303) 0K = 383,04 J
qtotal = q1 +q2+q3
= 10,08 J + 33,496 J + 383,04 J
= 426,616 J
H = qtotal / mole = 426,616 J / 0,138 mole
= 3091,42 J/mole = 3,091 kJ/mole

Composition B
Tconstant = 32 oC = 305 K
Mass of water = . V = 1 g/ml. 4 ml = 4 gram
T water = 30 C = 303 K
q1 = mw.c.T
= 4 g. 4,2 J/g 0K. (305 - 303) 0K = 33,6 J
Mass of ethanol = . V = 0,793 g/ml. 6 ml = 4,758 g
Mole of ethanol = m/Mr = 6,344 g/ 46 g/mole = 0,138 mole
Tethanol = 29 oC = 302 0K
q2 = me.c.T
= 6,344 g. 2,4 J/g 0K. (305 - 302) 0K = 45,6768 J
q3 = C. T
= 319,2 J/0K . (305 303) 0K = 638,4 J
qtotal = q1 +q2+q3
= 33,6 J + 45,6768 J + 638,4 J
= 717,6768 J
H = qtotal / mole = 717,6768 J / 0,138 mole
= 5200,56 J/mole = 5,2 kJ/mole

Composition C
Tconstant = 32 oC = 305 0K
Mass of water = . V = 1 g/ml. 6 ml = 6 gram
T water = 30 oC = 303 0K
q1 = mw.c.T
= 6 g. 4,2 J/g 0K. (305 - 303) 0K = 50,4 J
Mass of ethanol = . V = 0,793 g/ml. 4 ml = 3,172 g
Mole of ethanol = m/Mr = 3,172 g/ 46 g/mole = 0,069 mole
Tethanol = 29 oC = 302 0K
q2 = me.c.T
= 3,172g. 2,4 J/g 0K. (305 - 302) 0K = 22,8384 J
q3 = C. T
= 319,2 J/0K . (305 303) 0K = 638,4 J
qtotal = q1 +q2+q3
= 50,4 J + 22,8384 J + 638,4 J = 711,6384 J
H = qtotal / mole = 711,6384J / 0,069 mole
= 10313,6 J/mole = 10,31 kJ/mole
 Composition D
Tconstant = 31 oC = 304 0K
Mass of water = . V = 1 g/ml. 8ml = 8 gram
T water = 30 oC = 303 0K
q1 = mw.c.T
= 8 g. 4,2 J/g 0K. (304-303) 0K = 33,6 J
Mass of ethanol = . V = 0,793 g/ml. 2 ml = 1,586 g
Mole of ethanol = m/Mr = 1,586 g/ 46 g/mole = 0,034 mole
Tethanol = 29 oC= 302 0K
q2 = me.c.T
= 1,586g. 2,4 J/g 0K. (304 - 302) 0K = 7,6128 J
q3 = C. T
= 319,2 J/ 0K . (304 303) 0K = 319,2 J
qtotal = q1 +q2+q3
= 33,6 J + 7,6128 J + 319,2 J = 360,4128 J
H = qtotal / mole = 360,4128 / 0,034 mole
= 10600,376 J / mole = 10,6 kJ/mol
F. Discussion
1) Determination of calorimeter constant
In this experiment, we calculated the heat capacity(C) by a calorimeter,
cold water and hot water was mixed. The temperature of cold water was 29 C
and the temperature of hot water was 58 C. After 10 minutes, the constant
temperature that we got was 34C.
From this data, we could find :
q1 = 420 Joule
q2 = 2016 Joule
q3 = q1-q2 = 1596 Joule
also the heat capacity (C) C= 319,2 Joule/K

2) Neutralization heat of acid and base

In this experiment, we calculated the change of entalphy from the acid-
base solutions, we prepared acid solutions HCl (30C), CH3COOH (30C) and
base solutions NaOH (vC), NH4OH (29C).
a. NaOH and HCl were mixed for 5 minutes, and this mixture resulted the
constant temperature 32C, from this data we could find :
q4 = 734,184 Joule
q5 = 1437,75 Joule
q6 = q4+q5 = 2171,934 Joule
then H = q6/0,02 = 108596,7 J mol1=108,6 KJ1
 b. NaOH and CH3COOH were mixed for 5 minutes, and this mixture
resulted the constant temperature 31C, from this data we could find :
q4 = 706,2336 Joule
q5 = 1276,8 Joule
q6 = q4+q5 = 1983,0336 Joule
then H = q6/0,02 = 99151,68 Joule/mol = 99,2 KJ/mol

c. HCl and NH4OH were mixed for 5 minutes, and this mixture resulted
the constant temperature 30C, from this data we could find :
q4 = 732,492 Joule
q5 = 1436,4 Joule
q6 = q4+q5 = 2159,892 Joule
then H = q6/0,02 = 107994,6 Joule/mol = 107,9 KJ/mol

From this experiment we knew that the reactions is included Exoterm

reaction because during the mixed process, the temperature of solutions
before mixed and after mixed have changed and increased.

3) Heat dilution of ethanol in water

In this experiment, we calculated the change of entalphy by a calorimeter.
We prepared water (aquades) 30C, and the ethanol 29C. Both of them were
mixed for 4 minutes amount 10ml. This experiment divided by 4 parts:
a. Composition of this mixture consisted of 2ml of water and 8ml of
ethanol. After 4 minutes mixed, it resulted the constant temperature
31,2C. From this temperature we could find :
qw = 10,08 Joule
qe = 33,496 Joule
qcal= 383,04 Joule
qtot= qw + qe +qcal = 426,616 Joule
then H = 3091,42 J/mole = 3,091 kJ/mole

b. Composition of this mixture consisted of 4ml of water and 6ml of ethanol.

After 4 minutes mixed, it resulted the constant temperature 32C. From
this temperature we could find :
qw = 33,6 Joule
qe = 45,6768 Joule
qcal= 638,4 Joule
qtot= qw + qe +qcal = 717,6768 Joule
then H = 5200,56 J/mole = 5,2 kJ/mole
 c. Composition of this mixture consisted of 4ml of water and 6ml of ethanol.
After 4 minutes mixed, it resulted the constant temperature 32C. From
this temperature we could find :
qw = 50,4 Joule
qe = 22,8384 Joule
qcal= 638,4 Joule
qtot= qw + qe +qcal = 711,6384 Joule
then H = 10313,6 J/mole = 10,31 kJ/mol

d. Composition of this mixture consisted of 4ml of water and 6ml of ethanol.

After 4 minutes mixed, it resulted the constant temperature 31C. From
this temperature we could find :
qw = 33,6 Joule
qe = 7,6128 Joule
qcal= 319,2 Joule
qtot= qw + qe +qcal = 360,4128 Joule
then H = 10600,376 J/mol = 10,6 kJ/mol

G. Conclusion and recomendation

a) conclusion
1. The heat change can be determined (thermochemistry) with a calorimeter
2. Calorimeter constant can be found and determined by mixed cold water and hot water
in a calorimeter for few times and calculated it, C = 319,2 Joule/K
3. Change of entalphy reactions can be determined through this experiment by mixed
acid-base solutions and ethanol-water in a calorimeter for few times and calculated it :
Acid base solution:
1. 108,6 KJ1
2. 99,2 KJmol1
3. 107,9 KJ/mol
Water ethanol:
1. 3,091 kJ/mole
2. 5,2 kJ/mole
3. 10,31 kJ/mol
4. 10,6 kJ/mol
b) Recomendation
1. Look at the scala of thermometer carefully
2. Record the temperature as soon as possible
H. Source
http://en.wikipedia.org/wiki/Calorimeter
McMurry-Fay.2008.Chemistry. USA: Pearson Education.
http://www.chemistry.mcmaster.ca/~ayers/chem2PA3/labs/
CALORIMETRYINTRO.pdf
I. Questions
1. Determine the calorimeter constant by drawing graph showed relationship
between the temperature of the mixture of cold water and hot water vs time
intervals
2. Calculate the heat of neutralization of NaOH-HCl, NaOH-CH3COOH, HCl-
NH4OH by drawing graph showed relationship between the temperature of the
mixture of acid-base vs time intervals
3. Calculate the heat of dilution of ethanol in water based on the experimental

Answers :

1. Determination of calorimeter constant

35.2

35

34.8

34.6

34.4
Temperature 34.2
Hot water and Cold Water
34

33.8

33.6

33.4
1 2 3 4 5 6 7 8 9 10

Time interval

2. Determination of acid-baseneutralization heat

 35.2

35

34.8

34.6

34.4 NaOH - HCl

NaOH - CH3COOH
34.2
HCl - NH4OH
34

33.8

33.6

33.4
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5
3. Determination of heat dilution of ethanol in water
Composition A
Tconstant = 31,2 oC = 304,2 K
Mass of wate r = . V = 1 g/ml. 2 ml = 2 gram
T water = 30 C = 303 K
q1 = mw.c.T
= 2 g. 4,2 J/g 0K. (304,2 - 303) 0K = 10,08 J
Mass of ethanol = . V = 0,793 g/ml. 8 ml = 6,344 g
Mole of ethanol = m/Mr = 6,344 g/ 46 g/mole = 0,138 mole
Tethanol = 29 oC = 302 0K
q2 = me.c.T
= 6,344 g. 2,4 J/g 0K. (304,2 - 302) 0K = 33,496 J
q3 = C. T
= 319,2 J/0K . (304,2 303) 0K = 383,04 J
qtotal = q1 +q2+q3
= 10,08 J + 33,496 J + 383,04 J
= 426,616 J
H = qtotal / mole = 426,616 J / 0,138 mole
= 3091,42 J/mole = 3,091 kJ/mole

Composition B
Tconstant = 32 oC = 305 K
Mass of water = . V = 1 g/ml. 4 ml = 4 gram
T water = 30 C = 303 K
q1 = mw.c.T
= 4 g. 4,2 J/g 0K. (305 - 303) 0K = 33,6 J
Mass of ethanol = . V = 0,793 g/ml. 6 ml = 4,758 g
Mole of ethanol = m/Mr = 6,344 g/ 46 g/mole = 0,138 mole
Tethanol = 29 oC = 302 0K
q2 = me.c.T
= 6,344 g. 2,4 J/g 0K. (305 - 302) 0K = 45,6768 J
q3 = C. T
= 319,2 J/0K . (305 303) 0K = 638,4 J
qtotal = q1 +q2+q3
= 33,6 J + 45,6768 J + 638,4 J
= 717,6768 J
H = qtotal / mole = 717,6768 J / 0,138 mole
= 5200,56 J/mole = 5,2 kJ/mole

Composition C
Tconstant = 32 oC = 305 0K
Mass of water = . V = 1 g/ml. 6 ml = 6 gram
T water = 30 oC = 303 0K
q1 = mw.c.T
= 6 g. 4,2 J/g 0K. (305 - 303) 0K = 50,4 J
Mass of ethanol = . V = 0,793 g/ml. 4 ml = 3,172 g
Mole of ethanol = m/Mr = 3,172 g/ 46 g/mole = 0,069 mole
Tethanol = 29 oC = 302 0K
q2 = me.c.T
= 3,172g. 2,4 J/g 0K. (305 - 302) 0K = 22,8384 J
q3 = C. T
= 319,2 J/0K . (305 303) 0K = 638,4 J
qtotal = q1 +q2+q3
= 50,4 J + 22,8384 J + 638,4 J = 711,6384 J
H = qtotal / mole = 711,6384J / 0,069 mole
 = 10313,6 J/mole = 10,31 kJ/mole

Composition D
Tconstant = 31 oC = 304 0K
Mass of water = . V = 1 g/ml. 8ml = 8 gram
T water = 30 oC = 303 0K
q1 = mw.c.T
= 8 g. 4,2 J/g 0K. (304-303) 0K = 33,6 J
Mass of ethanol = . V = 0,793 g/ml. 2 ml = 1,586 g
Mole of ethanol = m/Mr = 1,586 g/ 46 g/mole = 0,034 mole
Tethanol = 29 oC= 302 0K
q2 = me.c.T
= 1,586g. 2,4 J/g 0K. (304 - 302) 0K = 7,6128 J
q3 = C. T
= 319,2 J/ 0K . (304 303) 0K = 319,2 J
qtotal = q1 +q2+q3
= 33,6 J + 7,6128 J + 319,2 J = 360,4128 J
H = qtotal / mole = 360,4128 / 0,034 mole
= 10600,376 J / mole = 10,6 kJ/mol
Documentation