7 Chapter 6
7 Chapter 6
7 Chapter 6
Chapter 6
Thermochemistry
Ahmad Aqel Ifseisi
Assistant Professor of Analytical Chemistry
College of Science, Department of Chemistry
King Saud University
P.O. Box 2455 Riyadh 11451 Saudi Arabia
Building: 05, Office: 2A/149 & AA/53
Tel. 014674198, Fax: 014675992
Web site: http://fac.ksu.edu.sa/aifseisi
E-mail: [email protected]
[email protected]
6.1
The nature of energy and
types of energy
Every chemical reaction obeys two fundamental laws:
- the law of conservation of mass, and
- the law of conservation of energy.
Unlike matter, energy is known and recognized by its effects. It cannot be
seen, touched, smelled or weighed.
Radiant energy
Thermal energy
Chemical energy
Potential energy
All forms of energy can be converted (at least in principle) from one form to another. When one
form of energy disappears, some other form of energy (of equal magnitude) must appear (law
of conservation of energy: the total quantity of energy in the universe is assumed constant).
6.2
Energy changes in
chemical reactions
Almost all chemical reactions absorb or produce (release) energy, generally in
the form of heat.
Heat is the transfer of thermal energy between two bodies that are at different
temperatures. Thus, we often speak of the “heat flow” from a hot object to a cold one.
We customarily talk of “heat absorbed” or “heat released” when describing the
energy changes that occur during a process.
Thermochemistry is the study of heat change in chemical reactions.
For chemists, systems usually include substances involved in chemical and physical changes.
There are three types of systems;
-An open system can exchange mass and energy, usually in the form of heat with its
surroundings. e.g., an open system may consist of a quantity of water in an open container.
-If we close the flask, so that no water vapor can escape from or condense into the container,
we create a closed system, which allows the transfer of energy (heat) but not mass.
-By placing the water in a totally insulated container, we can construct an isolated system,
which does not allow the transfer of either mass or energy.
-In exothermic reactions, the total energy of the products is less than the total
energy of the reactants. The difference is the heat supplied by the system to the
surroundings.
-In endothermic reactions, the difference between the energy of the products and
the energy of the reactants is equal to the heat supplied to the system by the
surroundings.
6.3
Introduction to
thermodynamics
Thermochemistry is part of a broader subject called thermodynamics, which is the
scientific study of the interconversion of heat and other kinds of energy.
Changes in state functions do not depend on the pathway, but only on the initial and final state.
The water could have reached room temperature from either direction. Therefore,
internal energy is a state function. It depends only on the present state of the system,
not on the path by which the system arrived at that state.
The conditions that influence internal energy include the temperature, pressure and
the total quantity of matter in the system because energy in an extensive property.
State function: depends only on the initial and final states of system, not on
how the internal energy is used.
We do not know the internal energy content of either the reactant molecules or the
product molecules, but we can accurately measure the change in energy content,
∆E, given by
∆E = E(product) – E(reactants)
= energy content of 1 mol SO2(g) – energy content of [1 mol S(s) + 1 mol O2(g)]
We find that this reaction gives off heat. Therefore, the energy of the product is less
than that of the reactants, and ∆E is negative.
The transfer of energy from the system to the surroundings does not change
the total energy of the universe. That is, the sum of the energy changes
must be zero:
∆Esys + ∆Esurr = 0
or
∆Esys = – ∆Esurr
where the subscripts “sys” and “surr” denote system and surroundings,
respectively.
When energy is exchanged between the system and the surroundings, it is
exchanged as either heat (q) or work (w).
E = q + w
Process Sign
Work done by the system on the surroundings –
Work done on the system by the surroundings +
Heat absorbed by the system from the surroundings (endothermic process) +
Heat absorbed by the surroundings from the system (exothermic process) –
w =Fxd
-e.g., when a gas is produced, then the gas produced can be used to push a piston,
thus doing work.
(a) Because the external pressure is zero, no work is done in the expansion.
w = -P∆V
= -(0)(6.0 - 2.0) L
=0
(b) The external, opposing pressure is 1.2 atm, so
w = -P∆V
= -(1.2 atm) (6.0 - 2.0) L To convert the answer to joules, we write
= -4.8 L·atm 1 L·atm = 101.3 J
w = -4.8 x 101.3 = -4.9 x 102 J
Practice Exercise
A gas expands from 264 mL to 971 mL at constant temperature. Calculate the work
done (in joules) by the gas if it expands (a) against a vacuum and (b) against a
constant pressure of 4.00 atm.
E = q + w
Heat and work are not state functions because they are not properties of a system.
They manifest themselves only during a process (during a change). Thus, their
values depend on the path of the process and vary accordingly.
But,,
∆E is a state function
∆E = q + w
= -128 J + 462 J
= 334 J
Practice Exercise
A gas expands and does P-V work on the surroundings equal to 279 J. At the same
time, it absorbs 216 J of heat from the surroundings. What is the change in energy
of the system?
EXAMPLE
Heat is transferred from the system to the surroundings, and work is done on the system by the
surroundings, so q is negative and w is positive: q = –1150 J and w = 480 kJ. Thus,
The negative value of ΔE tells us that a net quantity of 670 J of energy has been transferred
from the system to the surroundings.
6.4
Enthalpy of chemical
reactions
Constant Volume Processes
If a chemical reaction is run at constant volume, then
∆V = 0 and no P-V work will result from this change.
w = – P ∆V
∆E = q + w
∆E = q – P∆V
at constant volume; ∆V=0, so w=0
∆E = qv
∆E = q + w
= qp – P∆V
or
qp = ∆E + P∆V
where the subscript “p” denotes constant-pressure condition.
H = E + PV
where E is the internal energy of the system and P and V are the pressure and
volume of the system, respectively.
H = E + PV
Because E and PV have energy units, enthalpy also has energy units.
E, P, and V are all state functions, that is, the changes in (E + PV) depend only on
the initial and final states. It follows, therefore, that the change in H, or ∆H , also
depends only on the initial and final states. Thus, H is a state function.
∆H = ∆E + ∆(PV)
∆H = ∆E + P∆V
Enthalpy of Reactions
Because most reactions are constant-pressure processes, we can equate the heat
change in these cases to the change in enthalpy. For any reaction of the type
Reactants → Products
we define the change in enthalpy, called the enthalpy of reaction, ∆H, as the
difference between the enthalpies of the products and the enthalpies of the
reactants:
∆H = H(products) – H(reactants)
How much heat is released when 4.50 g of methane gas is burned in a constant
pressure system?
Solution
By adding the atomic weights of C and 4 H, we have 1 mol CH4 = 16.0 g CH4. We
can use the appropriate conversion factors to convert grams of CH4 to moles of CH4
to kilojoules:
The negative sign indicates that the system released 250 kJ into the surroundings.
EXAMPLE
calculate the heat evolved when 87.9 g of SO2 (molar mass = 64.07 g/mol)
is converted to SO3.
Practice Exercise
Calculate the heat evolved when 266 g of white phosphorus (P4) burns in air
according to the equation
∆E = ∆H – RT ∆n
where ∆n is defined as
∆n = (number of moles of product gases – number of moles of reactant gases)
For reactions that do not result in a change in the number of moles of gases
from reactants to products,
e.g.,
Practice Exercise
What is ∆E for the formation of 1 mole of CO at 1 atm and 25oC?
C(graphite) + ½O2(g) → CO(g) ∆H = -110.5 kJ/mol
The relationship between the heat capacity and specific heat of a substance is
C=ms
where m is the mass of the substance in grams. e.g., the specific heat of water is
4.184 J/g°C, and the heat capacity of 60.0 g of water is
(60.0 g) (4.184 J/g°C) = 251 J/°C
The equations for calculating the heat change are given by
q = m s ∆t
q = C ∆t
where:
q: the amount of heat that has been absorbed or released in a particular process.
∆t: is the temperature change; ∆t = tfinal – tinitial
The sign convention for q is the same as that for enthalpy change;
q is - positive for endothermic processes, and
- negative for exothermic processes.
The specific heats of some Substance Specific Heat (J/g °C)
common substances
Al 0.900
Au 0.129
C (graphite) 0.720
C (diamond) 0.502
Cu 0.385
Fe 0.444
Hg 0.139
H2O 4.184
CH3CH2OH 2.460
Notice that the specific heat of liquid water is higher than those of the other
substances listed. The high specific heat of water affects Earth’s climate because it
makes the temperatures of the oceans relatively resistant to change. It also is very
important in maintaining a constant temperature in our bodies.
EXAMPLE
Practice Exercise
An iron bar of mass 869 g cools from 94°C to 5°C. Calculate the heat
released (in kilojoules) by the metal.
6.6
Standard enthalpy of
formation and reaction
The reference point for all enthalpy expressions is called the standard
enthalpy of formation (∆Hof).
Substances are said to be in the standard state at 1 atm and 25oC, hence
the term “standard enthalpy.” The superscript ° represents standard-state
conditions (1 atm), and the subscript “f” stands for formation.
(a) 1 mol Na2O is formed from the elements sodium and oxygen in their proper states, solid Na and O2
gas, respectively. Therefore, the enthalpy change for reaction (a) corresponds to a standard enthalpy of
formation.
(b) Potassium is given as a liquid. It must be changed to the solid form, its standard state at 25oC.
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 equation for the formation reaction of 1 mol of
KCl(s) is
(c) The reaction 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 standard state of carbon at 25oC and 1 atm. The correct equation should be
6 C(graphite) + 6 H2(g) + 3 O2(g) → C6H12O6(s)
The standard enthalpy of formation of any element in its most stable form is zero.
-e.g., Molecular oxygen (O2) is more stable than the other allotropic form of oxygen, ozone (O3),
at 1 atm and 25°C. Thus, we can write ∆H°f (O2) = 0, but ∆H°f (O3) = 142.2 kJ/mol.
-e.g., graphite is a more stable allotropic form of carbon than diamond at 1 atm and 25°C, so we
have ∆H°f (C, graphite) = 0 and ∆H°f (C, diamond) = 1.90 kJ/mol.
Standard enthalpies of formation of some substances at 25°C
Substance ∆H°f (kJ/mol) Substance ∆H°f (kJ/mol)
O(g) 249.4 C2H2(g) acetylene 226.7
O2(g) 0 C6H6(l) benzene 49.0
O3(g) 142.2 C6H12O6(s) glucose -1273
Cl2(g) 0 C12H22O11(s) sucrose -2221
H2O2(l) -187.6 NH3 ammonia -46.19
H2O(g) -241.8 HF(g) -268.6
H2O(l) -285.8 HCl(g) -92.3
CO(g) -110.5 HBr(g) -36.23
CO2(g) -393.5 HI(g) 25.9
CH4(g) methane -74.8 NaCl(s) -410.9
C2H6(g) ethane -84.68 AgCl(s) -127
C3H8(g) propane -103.85 NaHCO3(s) sodium bicarbonate -947.7
CH3OH(l) methanol -238.6 Na2CO3(s) sodium carbonate -1130.9
C2H5OH(l) ethanol -277.7 CaCO3(s) calcium carbonate -1207.1
The importance of the standard enthalpies of formation is that once we know their
values, we can readily calculate the standard enthalpy of reaction, ∆Horxn, defined
as the enthalpy of a reaction carried out at 1 atm.
where m and n denote the stoichiometric coefficients for the reactants and products,
To use this Equation to calculate ∆H°rxn, we must know the ∆H°f values of the compounds that take
part in the reaction. These values can be determined by applying direct method or indirect method.
The Direct Method
This method of measuring ∆H°f works for compounds that can be readily
synthesized from their elements.
Example,,,
Because both graphite and O2 are stable allotropic forms of the elements,
Hess’s law stated that; when reactants are converted to products, the
change in enthalpy is the same whether the reaction takes place in one step
or in a series of steps.
However, burning graphite also produces some CO2, so we cannot measure the enthalpy
change for CO directly as shown. Instead, we must employ an indirect route, based on Hess’s
law. It is possible to carry out the following two separate reactions, which do go to completion:
Because chemical equations can be added and subtracted just like algebraic equations,
EXAMPLE
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements:
The equations for each step and the corresponding enthalpy changes are
EXAMPLE
This reaction is highly exothermic and the liquid iron formed is used to weld metals.
Calculate the heat released in kJ/g of Al reacted with Fe2O3.
∆H°f (Fe(l)) = 12.40 kJ/mol, ∆H°f (Al2O3(s)) = -1669.8 kJ/mol, ∆H°f (Fe2O3(s)) = -822.2 kJ/mol.
Calculate the standard enthalpy of formation of carbon disulfide (CS2) from its
elements, given that
Practice Exercise
Benzene (C6H6) burns in air to produce carbon dioxide and liquid water. Calculate
the heat released (in kilojoules) per gram of the compound reacted with oxygen.
The standard enthalpy of formation of benzene is 49.04 kJ/mol.