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THERMOCHEMISTRY
April 4th, 2017
A. Objective
1. Determine the heat change through a simple experiment
2. Determine the calorimeter constant
3. Determine the change of enthalpy reaction
B. Introduction
Thermochemistry is the branch of chemistry concerned with the heat effects that accompany
chemical reactions. To understand the relationship between heat and chemical and physical
changes, we must start with some basic definitions. We will then explore the concept of heat and
the methods used to measure the transfer of energy across boundaries. Another form of energy
transfer is work, and, in combination with heat, we will define the first law of thermodynamics. At
this point, we will establish the relationship between heats of reaction and changes in internal
energy and enthalpy. We will see that the tabulation of the change in internal energy and change in
enthalpy can be used to calculate, directly or indirectly, energy changes during chemical and
physical changes.
A system is the part of the universe chosen for study, and it can be as large as all the oceans
on Earth or as small as the contents of a beaker. Most of the systems we will examine will be
small and we will look, particularly, at the transfer of energy (as heat and work) and matter
between the system and its surroundings. The surroundings are that part of the universe outside the
systemwith which the system interacts. Three common systems:first, as we see them and, then, in
an abstract form that chemists commonlyuse. An open system freely exchanges energy and matter
with its surroundings. A closed system can exchange energy, but not matter, with its surroundings.
An isolated system does not interact with its surroundings (approximated). This summary of
observations in now known as the First Law of thermodynamics and is expressed as follow.
The remainder of this section says more, in a general way, about energy and its relationship to
work. Like many other scientific terms, energy is derived from Greek. It means “work within.”
Energy is the capacity to do work. Work is done when a force acts through a distance. Moving
objects do work when they slow down or are stopped. Thus, when one billiard ball strikes another
and sets it in motion, work is done. The energy of a moving object is called kinetic energy (the
word kinetic means “motion” in Greek). We can see the relationship between work and energy by
comparing the units for these two quantities.
Heat is energy transferred between a system and its surroundings as a result of a temperature
difference. Energy that passes from a warmer body (with a higher temperature) to a colder body
(with a lower temperature) is transferred as heat. At the molecular level, molecules of the warmer
body, through collisions, lose kinetic energy to those of the colder body. Thermal energy is
transferred—“heat flows”—until the average molecular kinetic energies of the two bodies become
the same, until the temperatures become equal. Heat, like work, describes energy in transit
between a system and its surroundings. Energy is required to overcome these attractive forces.
During the process of melting, the temperature remains constant as a thermal energy transfer
(heat) is used to overcome the forces holding the solid together. Aprocess occurring at a constant
temperature is said to be isothermal. Once a solid has melted completely, any further heat flow
will raise the temperature of the resulting liquid. (Determination n.d.)
Energy is usually defi ned as the capacity to do work. In Chapter 5 we defined work as “force
3 distance,” but we will soon see that there are other kinds of work. All forms of energy are
capable of doing work (that is, of exerting a force over a distance), but not all of them are equally
relevant to chemistry. The energy contained in tidal waves, for example, can be harnessed to
perform useful work, but the relationship between tidal waves and chemistry is minimal. Chemists
defi ne work as directed energy change resulting from a process. Kinetic energy—the energy
produced by a moving object—is one form of energy that is of particular interest to chemists.
Others include radiant energy, thermal energy, chemical energy, and potential energy.
Radiant energy, or solar energy, comes from the sun and is Earth’s primary energy source.
Solar energy heats the atmosphere and Earth’s surface, stimulates the growth of vegetation
through the process known as photosynthesis, and infl uences global climate patterns. Thermal
energy is the energy associated with the random motion of atoms and molecules. In general,
thermal energy can be calculated from temperature measurements.
The more vigorous the motion of the atoms and molecules in a sample of matter, the hotter
the sample is and the greater its thermal energy. However, we need to distinguish carefully
between thermal energy and temperature. A cup of coffee at 70°C has a higher temperature than a
bathtub fi lled with warm water at 40°C, but much more thermal energy is stored in the bathtub
water because it has a much larger volume and greater mass than the coffee and therefore more
water molecules and more molecular motion. (Chang n.d.)
When observing the heats of chemical reactions it is important to know which way the heat is
flowing in the chemical reaction. Is the heat being generated by the chemical reaction? Is heat
required in order for the chemical reaction to proceed? The following definitions are agreed upon
conventions describing the flow of heat in chemical reactions.
Exothermic Reactions is Chemical reactions that release heat to the surroundings are
considered to be exothermic reactions. Let’s look at the familiar combustion reaction of propane
(C3H8 ).
C3H8 + 5O2 → 3CO2 + 4H2 O
In truth this reaction is missing one very important product. C3H8(g)+ 5O2(g)→ 3CO2 (g)+
4H2O(g) + Heat . When one mole of propane is burned it releases 2028.8 kJ of heat to the
surroundings. Due to convention the heat of reaction for the combustion of propane is expressed
as -2028.8 kJ mol-1. The negative sign is from the perspective of the reactants. The propane and
the oxygen lost heat as a consequence of the combustion reaction.
Endothermic Reactions is Chemical reactions that need to absorb heat from the surroundings
in order to proceed are known as endothermic reactions. Let’s look at the formation of nitrogen
monoxide (NO) form nitrogen (N2) and oxygen (O2 ), N2(g) + O2(g) → 2NO(g) . Again this
chemical equation does not tell the entire story. The reaction will not proceed unless energy, in the
form of heat, is added to the reaction.
N2(g) + O2(g) + Heat → 2NO(g)
It is necessary for N2 and O2 to absorb 90.37 kJ mol-1 in order to react to form one mole of
NO. In the above balanced chemical equation twice that value, 180.74 kJ, were required to form
two moles of NO. By convention the heat of reaction for the formation of NO from N2 and O2 is
90.37 kJ mol-1 . This number is positive since the N2 and O2 are seen to have gained heat.
When an object or system of objects are heated more is going on than just the heating.
If you heat a beaker of water that is open to ambient pressure the volume of the water will
increase. This is a form of work know as P∆v work.
Rather than deal with this component of thermochemistry directly, a new value known as
enthalpy (H) was developed. Standard enthalpies of formation for many substances were
experimentally determined and listed in tables. It is easy to use these listed values to calculate the
change in enthalpy for a reaction using the following formula.
The three principle states of matter are solid, liquid, and gas. Below are listed the basic
definitions that differentiate these three states of matter from one another. Solids are materials that
have a definite shape and volume. The arrangement of atoms or molecules in a solid are fixed. The
movement of the atoms or molecules in a solid are very slow. Liquids are materials that have a
definite volume but an indefinite shape. The arrangement of liquid atoms or molecules is random.
The shape of a liquid is determined by the container holding the liquid. The movement of atoms
and molecules in a liquid is faster than they are in a solid. Gases are materials that have an
indefinite shape and volume. Both the shape and the volume of a gas are determined by the shape
and the volume of the container holding the gas. The arrangement of atoms or molecules in a gas
is random. The movement of atoms or molecules in a gas is very rapid. (Pitzer n.d.)
When two chemical equations are added or subtracted to yield a third equation, the heats of
reaction also can be added or subtracted with the usual algebraic conventions to yield the heat of
reaction for the third equation. In general, when references are made to thermodynamic quantities
like heat of formation, the implication is that be quaantity in question refers to 1 mole and term
molal will not be written explicity unless needed to avoid confusion. Small capital letters like H
are used to denite these molal quantities.
Actually the synthesis of glucose takes palce in a number of small steps. However, in the
overall process 673.0 kcal must enter the reacting materia in order to make the reaction take place
and form a product fa higher on the energy scale than the original reactants. The value of the
enthalpy change when a compound is formed from the elements under standard conditions is
called the standard entalphy of formation or the standard heat of formation. (Donald H. 1970)
D. Procedure
a. Calorimeter constant determination
Draw a graph to obtain the Mix NaOH and HCl in the calorimeter
temperature chaange due to this and record the temperature for 5 minute
reaaction with interval time ½ minute
Draw a graph to obtain the Mix NH4OH and HCl in the calorimeter
temperature chaange due to this and record the temperature for 5 minute
reaaction with interval time ½ minute
Put 2 mL water into the calorimeter and Put 8 mL ethanol into Graduated
record the temperature cylinders and record the temperature
E. Observation Sheet
a. Determination of calorimeter constant
Temperature of cold water (T1) in calorimeter = 26°C = 299 K
Temperature of hot water (T2) before being put into a calorimeter = 58°C = 331 K
Water temperature after mixing for 10 minutes at intervals of 1 minute
Temperature (°C)
35
34
33
32
1 2 3 4 5 6 7 8 9 10
Time intervals (min)
35
30
T NaOH – HCl (°C)
25
20
15
10
5
0
1 2 3 4 5 6 7 8 9 10
Time intervals (minutes)
35
30
T NaOH – CH3COOH (°C)
25
20
15
10
5
0
1 2 3 4 5 6 7 8 9 10
Time intervals (minutes)
25
15
10
0
1 2 3 4 5 6 7 8 9 10
Time intervals (minutes)
Composition A B C D
Volume of Water (mL) 2 4 6 8
Volume of Ethanol (mL) 8 6 4 2
Time intervals (minutes) 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Composition A 30 30 30 30 30 30 30 30
Temperature Composition B 29 29 29 29 29 29 29 29
(°C) Composition C 30 30 30 30 30 30 30 30
Composition D 29 29 29 29 29 29 29 29
F. Calculation
1. Determination of calorimeter constant
V1 = 20 mL 𝜌water = 1 g/mL
V2 = 20 mL cwater = 4,2 J/gK
T1 = 26°C = 299 K T2 = 58°C = 331 K
T3(constant) = 33°C = 306 K
Reaction :
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
M 0,02mol 0,02 mol - -
B 0,02mol 0,02 mol 0,02 mol 0,02 mol
S 0 0 0,02mol 0,02 mol
Vmix = VHCl + VNaOH
= 20 mL + 20 mL
= 40 mL
o ∆T3 = Tconstant – Ts
= 303 – 299
=4K
o ms = 𝜌s . vs
= 1,03 . 40
= 41,2 gram
q4 = ms . cs . ∆T3
= 41,2 . 3,96 . 4
= 652,608 J
q5 = Ccal . ∆T3
= 216 . 4
= 864 J
Reaction :
NaOH(aq) + CH3COOH(aq) CH3COONa(aq)+ H2O(l)
M 0,02mol 0,02 mol - -
B 0,02mol 0,02 mol 0,02 mol 0,02 mol
S 0 0 0,02mol 0,02 mol
o ∆T3 = Tconstant – Ts o ms = 𝜌s . vs
= 303 – 299 = 1,098 . 40
=4K = 43,92 gram
q4 = ms . cs . ∆T3
= 43,92 . 4,02 . 4
= 706,2336 J = 216 . 4
= 864 J
q5 = Ccal . ∆T3
Heat is produced by reaction ∆H =−
𝑞6
𝑛
q6 = q4 + q5 1570,2336
=−
= 706,2336 + 864 0,02
= 1570,2336 J = -78511,68 J/mol (exothermic)
Reaction :
NH4OH(aq) + HCl(aq) NH4Cl(aq) + H2O(l)
M 0,02mol 0,02 mol - -
B 0,02mol 0,02 mol 0,02 mol 0,02 mol
S 0 0 0,02mol 0,02 mol
o ∆T3 = Tconstant – Ts
= 301 – 299
=2K
o ms = 𝜌s . vs
= 1,015 . 40
= 40,6 gram
𝑇𝑤𝑎𝑡𝑒𝑟+𝑇𝑒𝑡ℎ𝑎𝑛𝑜𝑙
∆Tm = ∆T = ∆TConstant - ∆Tm
2
299 𝐾 +301 𝐾
= = (303 – 300) K
2
= 300 K =3K
q7 = mwater.cwater. ∆T
= 4 . 4,2 . 2
= 33,6 J
Heat is absorbed in ethanol
𝑔
Mass of ethanol = 𝜌ethanol .Vethanol molC2H5OH = 𝑀𝑟 C2H5OH
4,758 𝑔𝑟𝑎𝑚
= 0,793 g/mL . 6 mL = 46
= 4,758 gram = 0,1034mol
q8 = methanol. cethanol. ∆T
= 4,758. 1,92 . 2
= 18,27072 J
Heat is absorbed in calorimeter
q9 = Ckal . ∆T
= 216 . 2
= 432 J
q8 = methanol. cethanol. ∆T
= 3,172. 1,92 . 3
= 18,27072 J
q7 = mwater.cwater. ∆T
= 8 . 4,2 . 2
= 67,2 J
Heat is absorbed in ethanol
𝑔
Mass of ethanol = 𝜌ethanol .Vethanol molC2H5OH = 𝑀𝑟 C2H5OH
1,586 𝑔𝑟𝑎𝑚
= 0,793 g/mL . 2 mL = 46
= 1,586 gram = 0,0345mol
q8 = methanol. cethanol. ∆T
= 1,586 . 1,92 . 2
= 6.09024 J
Heat is absorbed in calorimeter Heat is produced by solution
q9 = Ckal . ∆T q10 = q7+ q8+ q9
= 216 . 2 = 60,2 + 6.09024 + 432
= 432 J = 498,29024 J
So, enthalpy change the heat of dilution of ethanol in water based on the experimental is :
∆HA + ∆HB + ∆HC + ∆HD
∆Hdilution = 4
− 514,68 +(− 4679,60) +(− 9009,59 ) +(−14443,20)
= 4
−28647,07
= 4
= - 7161,7675 J/mol (exothermic)
G. Discussion
1. Calorimeter constant determination
Calorimeter is an instrument used to measure the amount of heat involved in an alteration
or chemical reaction. Calorimeter is generally designed so that the system is in a state insulated
to prevent energy transfer or heat between the system and the environment. This experiment
aims to determine the constant of the calorimeter is used. The calorimeter constant is the amount
of heat that can be absorbed by the calorimeter per unit of temperature. The constant calorimeter
must be measured to determine the calorimeter constant or the amount of heat absorbed by the
calorimeter for each component have characteristic calorimeter to measure heat.
To determine the calorimeter constant, hot water and cold water with the same volume (20
mL) are mixed into the calorimeter, then stir and observed temperature for 10 minutes with an
interval of 1 minute after mixing. Stirring is done to accelerate the reaction between the hot and
cold water. Is the purpose of the cold water and hot water because cold water and calorimeter
will absorb heat and hot water to release heat. In this experiment, initial cold water temperature
measured in a calorimeter at 26, the temperature of hot water at 58 and the mixing temperature is
33. In the experiment this happens the exothermic process because the system release heat. This
is can be seen in the observation sheetwhich showed a increase in the temperature of the water
initially at 26°C up to 33°C for 10 minutes at intervals of 1 minutes after mixing.
This temperature drop can also be seen through the graph of the relationship between on the
temperature with the time interval in observation sheet.
In this experiment, we get the calculation result of heat absorbed by the cold water (q1) is
588 J, the absorbed heat hot water (q2) is 2100 J, and heat is absorbed calorimeter (q3) is 1512 J
. Calorimeter constants obtained from dividing the number of heat absorbed by the calorimeter
(q3) with ΔT then obtained a calorimeter constant rate is 216 J/K. Determination of the heat of
reaction calorimeter based on changes in solution temperature and the calorimeter with the
principles of heat transfer, the heat is given equal to the amount of heat absorbed.
H. Conclution
1. The heat change is the enthalpy change (∆H). The heat changes as a result of chemical
reactions can be measured in a calorimeter by measuring the temperature change.
2. The amount of heat absorbed by calorimeter to raise its temperature one degree is called the
calorimeter constant. So a unit calorimeter constant is JK-1. In this experiment, the
calorimeter constant is determined by mixing the “cold water” with “hot water” in the
calorimeter, and we get the result calorimeter constant rate (Ccal) is 216 J/K
3. In each experiment, the mixture between the two solutions is always experiencing changes
in temperature. The result of this experiment as the following:
a. HCl and NaOH
ΔH=-75830,4 J/mol (exothermic)
b. NaOH and CH3COOH
ΔH=-78511,68 J/mol (exothermic)
c. NH4OH and HCl
ΔH= -37677,6 J/mol (exothermic)
4. The maximum heat change occurs whwn ethanol is dissolved in an infinite volume of
water. This is called heat of dissolution or dissolution enthalpy. The result of this
experiment as the following:
a. 2 mL water and 8 mL ethanol
ΔH =- 514,68 J/mol (exothermic)
b. 4 mL water and 6 mL ethanol
ΔH = - 4679,60 J/mol (exothermic)
c. 6 mL water and 4 mL ethanol
ΔH = - 9009,59 J/mol (exothermic)
d. 8 mL water and 2 mL ethanol
ΔH = - 14443,20 J/mol (exothermic)
I. References
J. Appendiks
a. Problems
1. Determine to calorimeter constant by drawing a graph showed relationship between the
temperature of the mixture of cold water and hot water vs time intervals.
Answer :
Graph of Temperature vs Time Interval
36
Temperature (°C)
35
34
33
32
1 2 3 4 5 6 7 8 9 10
Time intervals (min)
V1 = 20 mL 𝜌water = 1 g/mL
V2 = 20 mL cwater = 4,2 J/gK
T1 = 26°C = 299 K T2 = 58°C = 331 K
T3(constant) = 33°C = 306 K
40
T NaOH – HCl (°C)
30
20
10
0
1 2 3 4 5 6 7 8 9 10
Time intervals (minutes)
THCl = 26°C = 299 K MHCl =1M
TNaOH = 26°C = 299 K MNaOH =1M
VHCl = 20 mL VNaOH = 20 mL
𝜌solution = 1,03 g/mL csolution = 3,96 Jg-1K-1
TConstant = 30°C = 303 K
Reaction :
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)
M 0,02mol 0,02 mol - -
B 0,02mol 0,02 mol 0,02 mol 0,02 mol
S 0 0 0,02mol 0,02 mol
o ∆T3 = Tconstant – Ts
= 303 – 299
=4K
o ms = 𝜌s . vs
= 1,03 . 40
= 41,2 gram
q4 = ms . cs . ∆T3
= 41,2 . 3,96 . 4
= 652,608 J
q5 = Ccal . ∆T3
= 216 . 4
= 864 J
Reaction :
NaOH(aq) + CH3COOH(aq) CH3COONa(aq)+ H2O(l)
M 0,02mol 0,02 mol - -
B 0,02mol 0,02 mol 0,02 mol 0,02 mol
S 0 0 0,02mol 0,02 mol
o ∆T3 = Tconstant – Ts o ms = 𝜌s . vs
= 303 – 299 = 1,098 . 40
=4K = 43,92 gram
q4 = ms . cs . ∆T3
= 43,92 . 4,02 . 4
= 706,2336 J
q5 = Ccal . ∆T3
= 216 . 4
= 864 J
20
10
0
1 2 3 4 5 6 7 8 9 10
Time intervals (minutes)
Reaction :
NH4OH(aq) + HCl(aq) NH4Cl(aq) + H2O(l)
M 0,02mol 0,02 mol - -
B 0,02mol 0,02 mol 0,02 mol 0,02 mol
S 0 0 0,02mol 0,02 mol
o ∆T3 = Tconstant – Ts
= 301 – 299
=2K
o ms = 𝜌s . vs
= 1,015 . 40
= 40,6 gram
𝑇𝑤𝑎𝑡𝑒𝑟+𝑇𝑒𝑡ℎ𝑎𝑛𝑜𝑙
∆Tm = ∆T = ∆TConstant - ∆Tm
2
299 𝐾 +301 𝐾
= = (303 – 300) K
2
= 300 K =3K
𝑇𝑤𝑎𝑡𝑒𝑟+𝑇𝑒𝑡ℎ𝑎𝑛𝑜𝑙
∆Tm = ∆T = ∆TContaant - ∆Tm
2
299 𝐾 +301 𝐾
= = (302 – 300) K
2
= 300 K =2K
Heat is absorbed in water
Mass of water = 𝜌water .Vwater
= 1 g/mL . 4 mL
= 4 gram
q7 = mwater.cwater. ∆T
= 4 . 4,2 . 2
= 33,6 J
Heat is absorbed in ethanol
𝑔
Mass of ethanol = 𝜌ethanol .Vethanol molC2H5OH = 𝑀𝑟 C2H5OH
4,758 𝑔𝑟𝑎𝑚
= 0,793 g/mL . 6 mL = 46
= 4,758 gram = 0,1034mol
q8 = methanol. cethanol. ∆T
= 4,758. 1,92 . 2
= 18,27072 J
Heat is absorbed in calorimeter
q9 = Ckal . ∆T
= 216 . 2
= 432 J
𝑇𝑤𝑎𝑡𝑒𝑟+𝑇𝑒𝑡ℎ𝑎𝑛𝑜𝑙
∆Tm = ∆T = ∆TConstant - ∆Tm
2
299 𝐾 +301 𝐾
= = (303 – 300) K
2
= 300 K =3K
q8 = methanol. cethanol. ∆T
= 3,172. 1,92 . 3
= 18,27072 J
𝑇𝑤𝑎𝑡𝑒𝑟+𝑇𝑒𝑡ℎ𝑎𝑛𝑜𝑙
∆Tm = ∆T = ∆TContaant - ∆Tm
2
299 𝐾 +301 𝐾
= = (302 – 300) K
2
= 300 K =2K
q8 = methanol. cethanol. ∆T
= 1,586 . 1,92 . 2
= 6.09024 J
Heat is absorbed in calorimeter Heat is produced by solution
q9 = Ckal . ∆T q10 = q7+ q8+ q9
= 216 . 2 = 60,2 + 6.09024 + 432
= 432 J = 498,29024 J
So, enthalpy change the heat of dilution of ethanol in water based on the experimental is :
∆HA + ∆HB + ∆HC + ∆HD
∆Hdilution = 4
− 514,68 +(− 4679,60) +(− 9009,59 ) +(−14443,20)
= 4
−28647,07
= 4
= - 7161,7675 J/mol (exothermic)
Documentation
Picture 1. Insert the cold water Picture 4. Record the hot water temperature
Picture 13. Put the ethanol Picture 16. Stiring the two solution