CHEMISTRY

The Central Science

Chapter 1
Thermochemistry

David P. White
1
 The Nature of Energy
Kinetic Energy and Potential Energy
• Kinetic energy is the energy of motion:
1 2
Ek  mv
2
• Potential energy is the energy an object possesses by
virtue of its position.
• Potential energy can be converted into kinetic energy.
Example: a bicyclist at the top of a hill.

2
 The Nature of Energy
Kinetic Energy and Potential Energy
• Electrostatic potential energy, Ed, is the attraction
between two oppositely charged particles, Q1 and Q2, a
distance d apart:
Q1Q2
Ed 
d
• The constant  = 8.99  109 J-m/C2. (a constant of
proportionality)
• If the two particles are of opposite charge, then Ed is the
electrostatic repulsion between them.
3
 The Nature of Energy
Kinetic Energy and Potential Energy
• When Q1 and Q2 have the same sign (Q1=+ve, Q2=+ve),
its repels each other, pushing them apart, then Ed is
positive.
• For opposite sign (Q1=+ve, Q2=-ve), they are attract
each other pulling them each other, then Ed is negative.

4
 The Nature of Energy
Units of Energy
• SI Unit for energy is the joule, J:
1 2 1
Ek  mv  2 kg 1 m/s 2
2 2
 1 kg - m/s 2  1 J

We sometimes use the calorie instead of the joule:

1 cal = 4.184 J (exactly)
A nutritional Calorie:
1 Cal = 1000 cal = 1 kcal 5
 The Nature of Energy
Systems and Surroundings
• System: part of the universe we are interested in.
• Surroundings: the rest of the universe.

6
 Definitions:
System and Surroundings
• The system includes the
molecules we want to
study (here, the hydrogen
and oxygen molecules).
• The surroundings are
everything else (here, the
cylinder and piston).

© 2009, Prentice-Hall, Inc.

 The Nature of Energy
Transferring Energy: Work and Heat
• Force is a push or pull on an object.
• Work is the product of force applied to an object over a
distance:
w  F d
• Energy is the work done to move an object against a
force.
• Heat is the transfer of energy between two objects.

• Therefore, Energy is the capacity to do work or transfer

heat.
8
Heat

• Energy can also be

transferred as heat.
• Heat flows from
warmer objects to
cooler objects.

© 2009, Prentice-Hall, Inc.

 The First Law of
Thermodynamics
Internal Energy
• Internal Energy: total energy of a system.
• Cannot measure absolute internal energy.
• Change in internal energy,
E  Efinal  Einitial

10
 The First Law of
Thermodynamics
Relating E to Heat and Work
• Energy cannot be created or destroyed.
• Energy of (system + surroundings) is constant.
• Any energy transferred from a system must be transferred
to the surroundings (and vice versa).
• From the first law of thermodynamics:
when a system undergoes a physical or chemical change, the
change in internal energy is given by the heat added to or
absorbed by the system plus the work done on or by the
system: E  q  w
11
The First Law of
Thermodynamics

12
13
 The First Law of
Thermodynamics
Exothermic and Endothermic
Processes
• Endothermic: absorbs heat from the surroundings.
• Exothermic: transfers heat to the surroundings.
• An endothermic reaction feels cold.
• An exothermic reaction feels hot.

14
 Exchange of Heat between
System and Surroundings
• When heat is absorbed by the system from
the surroundings, the process is endothermic.

© 2009, Prentice-Hall, Inc.

 Exchange of Heat between
System and Surroundings
• When heat is absorbed by the system from
the surroundings, the process is endothermic.
• When heat is released by the system into the
surroundings, the process is exothermic.

© 2009, Prentice-Hall, Inc.

 The First Law of
Thermodynamics
State Functions
• State function: a property of a system that depends only
on the initial and final states of system, not on how the
internal energy is used. (…depends only on the physical state (P,T,
etc) of the system and not on the route used to achieve the current state).

17
 State Functions

• However, q and w are not state functions.

• Whether the battery is shorted out or is discharged by
running the fan, its E is the same. 18
 Enthalpy
• Chemical reactions can absorb or release heat.
• However, they also have the ability to do work.
• For example, when a gas is produced, then the gas
produced can be used to push a piston, thus doing work.
Zn(s) + 2H+(aq)  Zn2+(aq) + H2(g)
• The work performed by the above reaction is called
pressure-volume work.
• When the pressure is constant, w   PV
(when work is done on the surrounding,
w<0 or negative, and when work is done by
the surrounding w>0 and positive.) 19
 Enthalpy

When V is positive, work w is negative indicate that work is

done on the surrounding
When V is negative, work w is positive indicate that work is
done by the surrounding 20
 Enthalpy
• Enthalpy, H: Heat transferred between the system and
surroundings carried out under constant pressure.
H  E  PV
(internal energy + the product of the pressure and
volume of the system)
• Enthalpy is a state function because E, P & V are all state
functions.
• If the process occurs at constant pressure,
H   E  PV 
 E  PV
21
 Enthalpy
• Since we know that w   PV

• We can write H  E  PV

 qP  w  w  q p

• When H, is positive, the system gains heat from the

surroundings. (endothermic)
• When H, is negative, the surroundings gain heat from
the system. (exothermic)

22
Enthalpy

23
 Enthalpies of Reaction

• For a reaction:
H  H final  H initial
 H products  H reactants
• Enthalpy is an extensive property (magnitude H is
directly proportional to amount):
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = -802 kJ
2CH4(g) + 4O2(g)  2CO2(g) + 4H2O(g) H = 1604 kJ

24
 Enthalpies of Reaction
• When we reverse a reaction, we change the sign of H:
CO2(g) + 2H2O(g)  CH4(g) + 2O2(g) H = +802 kJ

• Change in enthalpy depends on state:

2H2O(g)  2H2O(l) H = -88 kJ

H2O(l)  H2O(g) H = +44 kJ

H2O(s)  H2O(l) H = +6.01 kJ

25
 Calorimetry
Heat Capacity and Specific Heat
• Calorimetry = measurement of heat flow by expt
• Calorimeter = apparatus that measures heat flow.
• Heat capacity = the amount of energy required to raise
the temperature of an object (by one degree).
• Molar heat capacity = heat capacity of 1 mol of a
substance.
• Specific heat = specific heat capacity = heat capacity of 1
g of a substance.
q  specific heat   grams of substance   T
26
 Calorimetry
Constant Pressure Calorimetry
• Atmospheric pressure is constant!
H  qP
qrxn  qsoln  specific heat of solution 
 grams of solution   T

27
 Calorimetry
Constant Pressure Calorimetry

28
 Calorimetry
Bomb Calorimetry (Constant Volume
Calorimetry)

• Reaction carried out under

constant volume.
• Use a bomb calorimeter.
• Usually study combustion.

qrxn  Ccal  T

• Ccal is the heat capacity of

the calorimeter.
29
 Hess’s Law

• Hess’s law: if a reaction is carried out in a number of

steps, H for the overall reaction is the sum of H for
each individual step.
• For example:
CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) H = -802 kJ
2H2O(g)  2H2O(l) H = -88 kJ
CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) H = -890 kJ

30
 Hess’s Law

Note that:
H1 = H2 + H3

31
SAMPLE EXERCISE 5.8 Using Hess’s Law to Calculate H

The enthalpy of reaction for the combustion of C to CO2 is – 393.5 kJ/mol C, and the enthalpy for the
combustion of CO to CO2 is – 283.0 kJ/mol CO:

Using these data, calculate the enthalpy for the combustion of C to CO:

Solution
In order to use equations (1) and (2), we arrange them so that C(s) is on the reactant side and CO(g)
is on the product side of the arrow, as in the target reaction, equation (3). Because equation (1) has
C(s) as a reactant, we can use that equation just as it is. We need to turn equation (2) around,
however, so that CO(g) is a product. Remember that when reactions are turned around, the sign of H
is reversed. We arrange the two equations so that they can be added to give the desired equation:

32
SAMPLE EXERCISE 5.8 continued

When we add the two equations, CO2(g) appears on both sides of the arrow and therefore cancels out.
Likewise, is eliminated from each side.

33
SAMPLE EXERCISE 5.9 Using Three Equations with Hess’s Law to Calculate H

Calculate H for the reaction

given the following chemical equations and their respective enthalpy changes:

Solution
Analyze: We are given a chemical equation and asked to calculate its H using three chemical
equations and their associated enthalpy changes.
Plan: We will use Hess’s law, summing the three equations or their reverses and multiplying each by
an appropriate coefficient so that they add to give the net equation for the reaction of interest. At the
same time, we keep track of the H values, reversing their signs if the reactions are reversed and
multiplying them by whatever coefficient is employed in the equation.
Solve: Because the target equation has C2H2 as a product, we turn the first equation around; the
sign of H is therefore changed. The desired equation has 2 C(s) as a reactant, so we multiply the
second equation and its H by 2. Because the target equation has as a reactant, we keep the third
equation as it is. We then add the three equations and their enthalpy changes in accordance with
Hess’s law:

34
SAMPLE EXERCISE 5.9 continued

When the equations are added, there are on both sides of the arrow. These
are canceled in writing the net equation.

35
 Enthalpies of Formation

• If 1 mol of compound is formed from its constituent

elements, then the enthalpy change for the reaction is
called the enthalpy of formation, Hof .
• Standard conditions (standard state): 1 atm and 25oC
(298 K).
• Standard enthalpy, Ho, is the enthalpy measured when
everything is in its standard state.
• Standard enthalpy of formation: 1 mol of compound is
formed from substances in their standard states.
36
 Enthalpies of Formation

• If there is more than one state for a substance under

standard conditions, the more stable one is used.
• Standard enthalpy of formation of the most stable form of
an element is zero.

37
Enthalpies of Formation

38
 Enthalpies of Formation
Using Enthalpies of Formation to
calculate Enthalpies of Reaction
• We use Hess’ Law to calculate enthalpies of a reaction
from enthalpies of formation.

39
40
 Enthalpies of Formation
Using Enthalpies of Formation to
calculate Enthalpies of Reaction
• For a reaction
H rxn   nH f products    mH f reactants 

41
SAMPLE EXERCISE 5.10 Identifying Equations associated with Enthalpies of Formation

For which of the following reactions at 25°C would the enthalpy change represent a standard enthalpy
of formation? For those where it does not, what changes would need to be made in the reaction
conditions?

Solution
Analyze: The standard enthalpy of formation is represented by a reaction in which each reactant is
an element in its standard state and the product is one mole of the compound.
Plan: To solve these problems, we need to examine each equation to determine, first of all, whether
the reaction is one in which a substance is formed from the elements. Next, we need to determine
whether the reactant elements are in their standard states.
Solve: In (a) Na2O is formed from the elements sodium and oxygen in their proper states, a solid
and O2 gas, respectively. Therefore, the enthalpy change for reaction (a) corresponds to a standard
enthalpy of formation.
In (b) potassium is given as a liquid. It must be changed to the solid form, its standard state at
room temperature. Furthermore, two moles of product are formed, so the enthalpy change for the
reaction as written is twice the standard enthalpy of formation of KCl(s). The proper equation for the
formation reaction is

42
SAMPLE EXERCISE 5.10 continued

Reaction (c) does not form a substance from its elements. Instead, a substance decomposes to its
elements, so this reaction must be reversed. Next, the element carbon is given as diamond, whereas
graphite is the lowest-energy solid form of carbon at room temperature and 1 atm pressure. The
equation that correctly represents the enthalpy of formation of glucose from its elements is

43
SAMPLE EXERCISE 5.11 Calculating an Enthalpy of Reaction from
Enthalpies of Formation

(a) Calculate the standard enthalpy change for the combustion of 1 mol of benzene, C6H6(l), to CO2(g)
and H2O(l). (b) Compare the quantity of heat produced by combustion of 1.00 g propane to that
produced by 1.00 g benzene.

Solution
Analyze: (a) We are given a reaction [combustion of C6H6(l) to form CO2(g) and H2O(l)] and asked
to calculate its standard enthalpy change, H° (b) We then need to compare the quantity of heat
produced by combustion of 1.00 g C6H6 with that produced by 1.00 g of C3H8, whose combustion was
treated above in the text.
Plan: (a) We need to write the balanced equation for the combustion of C6H6. We then look up
values in Appendix C or in Table 5.3 and apply Equation 5.31 to calculate the enthalpy change for the
reaction. (b) We use the molar mass of C6H6 to change the enthalpy change per mole to that per
gram. We similarly use the molar mass of C3H8 and the enthalpy change per mole calculated in the
text above to calculate the enthalpy change per gram of that substance.

Solve: (a) We know that a combustion reaction involves O2(g) as a reactant. Thus, the balanced
equation for the combustion reaction of 1 mol C6H6(l) is

44
SAMPLE EXERCISE 5.11 continued

We can calculate H° for this reaction by using Equation 5.31 and data in Table 5.3. Remember to
multiply the
value for each substance in the reaction by that substance’s stoichiometric coefficient. Recall
also that
for any element in its most stable form under standard conditions, so

(b) From the example worked in the text, Hº = –2220 kJ for the combustion of 1 mol of propane. In
part (a) of this exercise we determined that H° = –3267 kJ for the combustion of 1 mol benzene. To
determine the heat of combustion per gram of each substance, we use the molar masses to convert
moles to grams:

Comment: Both propane and benzene are hydrocarbons. As a rule, the energy obtained from the
combustion of a gram of hydrocarbon is between 40 and 50 kJ.

45
 Foods and Fuels
Foods
• Fuel value = energy released when 1 g of substance is
burned.
• 1 nutritional Calorie, 1 Cal = 1000 cal = 1 kcal.
• Energy in our bodies comes from carbohydrates and fats
(mostly).
• Intestines: carbohydrates converted into glucose which
react with O2 to produce energy.
C6H12O6 + 6O2  6CO2 + 6H2O, H = -2816 kJ
• Fats break down as follows:
2C57H110O6 + 163O2  114CO2 + 110H2O, Ho = -75,520 kJ
46
 Foods and Fuels

Foods
• Fats: store excess energy; are insoluble in water, so are
good for energy storage.

47
 Foods and Fuels
Fuels
• In 2000 the United States consumed 1.03  1017 kJ of
fuel.
• Most fuel derived from petroleum and natural gas.
• Remainder from coal, nuclear, and hydroelectric.
• Fossil fuels are not renewable.

48
Foods and
Fuels

49
 Foods and Fuels
Fuels
• Fuel value = energy released when 1 g of substance is
burned.
• Hydrogen has great potential as a fuel with a fuel value of
142 kJ/g.

50
 Lattice Energy in Ions

• Each Cl- ion is surrounded by six Na+ ions in NaCl

molecules
• There is a regular arrangement of Na+ and Cl- in 3D.
• Note that the ions are packed as closely as possible.
• Note that it is not easy to find
a molecular formula to describe
the ionic lattice.

51
 Energetics of Ionic Bond
Formation
• The formation of Na+(g) and Cl-(g) from Na(g) and
Cl(g) is endothermic.
• Why is the formation of Na(s) exothermic?
• The reaction NaCl(s)  Na+(g) + Cl-(g) is endothermic
(H = +788 kJ/mol).
• The formation of a crystal lattice from the ions in the
gas phase is exothermic:
Na+(g) + Cl-(g)  NaCl(s) H = -788 kJ/mol
52
 Lattice Energy

• Lattice energy: the energy required to completely

separate a mole of an ionic solid into its gaseous ions.
• Lattice energy depends on the charges on the ions and
the sizes of the ions:
Q1Q2
El  
d
к is a constant (8.99 x 109 J·m/C2), Q1 and Q2 are the
charges on the ions, and d is the distance between ions.

53
• Lattice energy increases as
- the charges on the ions increase
- the distance between the ions decreases.

54
 Sample Exercise 8.1 Magnitudes of Lattice Energies

Without consulting Table 8.2, arrange the following ionic compounds in order of increasing
lattice energy: NaF, CsI, and CaO.
Solution
Analyze: From the formulas for three ionic compounds, we must determine their relative
lattice energies.
Plan: We need to determine the charges and relative sizes of the ions in the compounds.
We can then use Equation 8.4 qualitatively to determine the relative energies, knowing
that the larger the ionic charges, the greater the energy and the farther apart the ions are,
the lower the energy.
Solve: NaF consists of Na+ and F– ions, CsI of Cs+ and I– ions, and CaO of Ca2+ and O2–
ions. Because the product of the charges, Q1Q2, appears in the numerator of Equation
8.4, the lattice energy will increase dramatically when the charges of the ions increase.
Thus, we expect the lattice energy of CaO, which has 2+ and 2– ions, to be the greatest
of the three.
The ionic charges in NaF and CsI are the same. As a result, the difference in their lattice
energies will depend on the difference in the distance between the centers of the ions in
their lattice. Because ionic size increases as we go down a group in the periodic table
(Section 7.3), we know that Cs+ is larger than Na+ and I– is larger than F–. Therefore the
distance between the Na+ and F– ions in NaF will be less than the distance between the
Cs+ and I– ions in CsI. As a result, the lattice energy of NaF should be greater than that of
CsI. In order of increasing energy, therefore, we have CsI < NaF < CaO.
Check: Table 8.2 confirms our predicted order is correct. 55
End of Chapter 1:
Thermochemistry

56