Thermo Chemistry

U N IVERSIT Y OF IN D ON ESIA
Thermochemistry
Thermochemistry
The Nature of Energy

The First Law of Themodynamics
Enthalpy
Entalphies of Reaction
Calorimetry
Hesss Law
Entalphies of Formation
Foods and Fuels
Thermochemistry
Termokimia
Thermochemistry
The Nature of
Energy
Energy can be defined as the capacity

to do work or
to transfer heat.
Matter possesses energy both

by virtue of its motion (kinetic energy) and
by virtue of its position (potential energy).
Thermochemistry is the study of the transfer of

energy from one sample of matter to another in the
form of heat or work.
The Nature of
Energy
The SI unit of energy is the joule.

One joule is the amount of kinetic energy possessed
by a 2 kilogram object moving at a speed of one
meter per second:
where mass is 2 kilograms and velocity is 1 meter per
second.
Thus, the joule is a derived SI unit.
The Nature of
Energy
Calorie - the amount of energy necessary to raise the

temperature of 1 g of water by 1oC.
1 cal = 4.184 J.
Nutritional calorie (Calorie);
1 Cal = 1000 cal = 1 kcal = 4.184 kJ.
The Nature of
Energy
The study of thermochemistry requires the definition

of
system and
surroundings.
The system is the particular sample of matter under

investigation, and the surroundings include
everything else outside the system.
surroundings
system
The Nature of
Energy
The Nature of
Energy
Energy
The Nature of
Energy
The First Law of

Themodynamics
Although kinetic energy can be converted

to potential energy, and vice versa, the total amount
of energy possessed by the system and surroundings
remains constant.
This is the first law of thermodynamics.
Energy can be neither created nor destroyed.
It can only be converted from one form into another
The First Law of

Themodynamics
The First Law of

Themodynamics
The First Law of

Themodynamics
The ball of clay in Figure 6.1 possesses potential

energy by virtue of its position and Earth's
gravitational pull.
When the ball of clay falls off the brick wall, some of
its potential energy is converted to kinetic energy.
The First Law of

Themodynamics
As it falls, it has kinetic energy by virtue of its mass

and its velocity.
When the ball hits the ground, part of the kinetic
energy it possessed during the fall is used to squash
it on impact.
The rest of the energy is released as heat.
The First Law of

Themodynamics
Many forms of energy:

Thermal energy.
Heat - energy transferred from one object to another as
the result of a temperature difference between them.
Temperature - a measure of the kinetic energy of
molecular motion.
Chemical energy - a type of potential energy in which the
chemical bonds of molecules act as the storage medium.
The First Law of

Themodynamics
Energy is conserved.
The total energy possessed by a system is the
system's internal energy, E.
Although it generally is not possible to
determine the exact value of E, it is possible to
measure changes in E associated with
chemical or physical processes.
This is made possible by the fact that E is
a state function.
The First Law of

Themodynamics
State Functions
a function or property whose value depends only
on the present state (condition) of the system, not
on the path used to arrive at that condition.
State functions are reversible.

For any state function, the overall change is
zero if the system returns to its original
condition.
The First Law of

Themodynamics
The change in internal energy associated with a

process is related to heat and work by the equation
q is heat transferred and w is work done.
The First Law of

Themodynamics
By convention,
when heat is transferred to the system from
surroundings, q is a positive number.
When heat flows from system to surroundings, q
negative number.
Similarly, when the surroundings do work on
system, w is positive,
nd when the system does work on the surroundings,
negative.
the
is a
the
w is
The First Law of

Themodynamics
Work the force (f) that produces the movement of

an object times the distance moved (d).
Expansion work (PV work) - work done as the result
of a volume change in the system.
w = -(P x V)
The First Law of

Themodynamics
Expansion of the system.

a. system does work on the surroundings
b. E is negative
c. w = -PV
i. work is negative
ii. V is positive
The First Law of

Themodynamics
Contraction of the system.

a. surroundings do work on the system
b. E is positive
c. w = -PV
i. work is positive
ii. V is negative
The First Law of

Themodynamics
Calculate the amount of work done during a

reaction in which a volume change from 28.3 L
to 35.7 L occurs. What is the direction of
work? The external pressure in the reaction is
9.3 atm.
w = -PV
w = - (9.3 atm) (35.7 L 28.3 L) = -69 atmL
The First Law of

Themodynamics
Most of the material in this chapter is concerned

with heat transfer rather than work.
An exothermic process is one that results in heat
being transferred from the system to the
surroundings.
An endothermic processresults in heat being
transferred from the surroundings to the system.
Enthalpy
The internal energy of a system can be divided into
two parts:
The capacity to do pressure-volume work, PV (recall that
when work is done by the system, the sign of w is
negative);
and the capacity to transfer heat, known as
the enthalpy, H.
The relationship between internal energy and

enthalpy is
Enthalpy
Like internal energy, enthalpy itself cannot be
determined exactly, but changes in enthalpy (H) can
be determined.
Many chemical reactions are carried out at constant
pressure.
For a constant-pressure process, the changes in
internal energy and enthalpy are related by the
equation
Enthalpy
In addition to being carried out at constant pressure,
many reactions (particularly those carried out in
solution) exhibit a negligible volume change.
In this case the term P V is essentially zero, and the
values of E and H are essentially equal.
The change in enthalpy, H, is the heat exchanged
between system and surroundings as the result of a
process carried out at constant pressure: H = qP.
Enthalpy
According to the sign convention,
an exothermic process will have a negative H and
an endothermic process will have a positive H.
Enthalpy, like internal energy, is a state function.
Enthalpy
Important Facts About Enthalpy
Enthalpy is an extensive property
The enthalpy change of a reaction is equal in magnitude

but opposite in sign to the enthalpy change of the reverse
reaction
The enthalpy change of a reaction depends on the states
of matter of the products and reactants
Enthalpy
Workgas
Enthalpy
Enthalpy
Enthalpy
Enthalpy
Changes of State
Enthalpies
A. Total energy change of a system.
E = q + w (q = heat).
E = q + (-PV).
B. Amount of heat transferred.

q = E + PV.
Enthalpies
C. Reactions carried out with constant volume.
V = 0; no PV work is done.
qv = E.
D. Reactions carried out at constant pressure.

V 0; energy change due to both heat transfer and PV
work.
qp = E + PV.
Enthalpies
Enthalphy
Enthalpies of
Reaction
Also known as the heat of reaction, the enthalpy of

reaction (Hrxn) is the heat exchanged between
system and surroundings at constant pressure, as the
result of a chemical reaction.
H's can also be written for physical processes, and a
subscript abbreviating the specific process is typically
included.
For example, the heat required to vaporize a mole of
substance is referred to as Hvap, the delta H of
vaporization or the heat of vaporization of that substance.
Enthalpies of
Reaction
Also known as the heat of reaction, the enthalpy of

reaction (Hrxn) is the heat exchanged between
system and surroundings at constant pressure, as the
result of a chemical reaction.
Enthalpies of
Reaction
H's can also be written for physical processes, and a

subscript abbreviating the specific process is typically
included.
For example, the heat required to vaporize a mole of
substance is referred to as Hvap, the delta H of
vaporization or the heat of vaporization of that substance.
Enthalpies of
Reaction
If the reactants in a chemical reaction have a greater

enthalpy (heat content) than the productsthe
reactants have to give off heat in order to become
productsthe sign of H will be negative.
A negative Hcorresponds to an exothermic process.
Conversely, a positive
H corresponds to an
endothermic process.
Enthalpies of
Reaction
Hsolution, sometimes called heat of solution or

molar enthalpy of dissolution, refers to
the Hrxn for the physical process of dissolving
one mole of a substance in water.
Enthalpy
Thermite
Enthalpies of
Reaction
H heat of reaction Enthalpy of a system name given to the quantity E + PV.

Enthalpy change of a system
H = E + PV.
State function value depends only on the
current state of the system.
H = Hproducts Hreactants.
Amount of heat released in a specific reaction
depends on the actual amounts of reactants.
Enthalpies of
Reaction
The value of the enthalpy change H reported

for a reaction represents the amount of heat
released when reactants are converted to
products in the molar amounts represented by
coefficients of the balanced equation.
The actual amount of heat involved in a reaction
depends on the actual amounts of reactants.
The physical states of reactants and products must be
specified.
Temperature and pressure also must be reported.
Enthalpies of
Reaction
Thermodynamic Standard State 298.15 K

(25o C) 1 atm pressure of each gas, 1 M
concentration (for solutions)
Allows different reactions to be compared.
Indicated by addition of a superscript o, Ho.
Standard enthalpy of reaction an enthalpy

change measured under standard conditions.
Enthalpies of
Reaction
EXAMPLE:
What is the value of Eo if a reaction having
Ho = 135.3 kJ is carried out at a constant
pressure of 18.9 atm and the volume change
is 238 L?
Enthalpies of
Reaction
Solution:
Ho = Eo + PV
Before solving for Eo, we must give serious
consideration to our units.
Keep in mind that the units for Ho are kJ
while the units for PV are L atm.
Obviously, we would like all of our units to be
energy units.
Enthalpies of
Reaction
A detailed study of conversion factors found

on the back cover, leads us to the following:
Enthalpies of
Reaction
Enthalpies of physical change.

Heat of fusion - the amount of heat required for
melting.
Heat of vaporization - amount of heat required for
evaporation.
Sublimation - the direct conversion of a solid to a
vapor without going through a liquid state.
a. heat of sublimation = heat of fusion + heat of
vaporization
Enthalpy
Enthalpies of
Reaction
Enthalpies of chemical change.

Heats of reaction - enthalpies of chemical change.
Endothermic reactions.
Hproducts > Hreactants
heat flow into the system from the surroundings
H is positive
Exothermic reactions.
Hproducts < Hreactants
heat flow to the surroundings from the system
H is negative
Enthalpies of
Reaction
Ho values for a given equation.

the equation is balanced for the number of moles
of reactants and products
all substances are in their standard states
physical state of each substance is specified
refer to the reaction going in the direction written
reverse the direction of the reaction, change the sign of
Ho
Calorimetry
Thermochemical experiments are carried out using
calorimetry, which allows the measuring of heat flow.
The value of H can be determined experimentally
by measuring the heat flow accompanying a reaction
at constant pressure.
Experimentally, we can determine the heat flow
associated with a chemical reaction by measuring
the temperature change it produces.
The measurement of heat flow is calorimetry
Calorimetry
An apparatus that measures heat flow is a
calorimeter.
Heat capacity and specific heat
Constant-pressure calorimetry
Bomb calorimetry (constant-volume
calorimetry)
Calorimetry
Heat capacity: quantity of heat required to
raise temperature of a sample of matter by 1 K
( 1 oC)
Specific heat: heat capacity of 1 g of a sample
heat capacity applies to objects, while molar
and specific heat capacities apply to
substances
quantity of heat transferred
Specific heat =
(g of substance) (temperature change )
q
=
m T
Calorimetry
Calorimetry
The heat capacity of 1 mol of a substance is
called its molar heat capacity.
This is simply the amount of heat necessary to
raise the temperature of 1 mol of
a substance by one degree.
The units of molar heat capacity are joules per
mole per degree, J/mol-C or J/mol-K.
Calorimetry
Specific heat, also known as specific heat
capacity, is defined as the amount of heat
necessary to raise the temperature of 1 g of a
substance by one degree.
The units of specific heat are joules per gram
per degree, J/g-C or J/g-K.
Calorimetry
Note that heat capacity applies to objects,
while molar and specific heat capacities apply
to substances.
Note also that the units of each can specify
degrees Celsius or Kelvin, since the magnitude
of a degree is the same on both scales.
Calorimetry
The device used to measure heat flow
between systems and surroundings is called
a calorimeter.
Two kinds of calorimetry:
constant-pressure calorimetry and
constant-volume, or "bomb," calorimetry.
Calorimetry
Calorimetry
A simple coffee-cup calorimeter

can be used to measure the
heat produced (or consumed)
by a reaction that takes place in
solution.
Calorimetry
25.00 mL each of aqueous 0.1000 M HCl and
0.1000 M NaOH at an initial temperature of
22.00C are mixed in a coffee-cup calorimeter
(Figure 5.16). Neutralization takes place by the
reaction:
Calorimetry
Given that the Hneutralization for this reaction is
55.83 kJ, what will be the final temperature
of the solution? (Assume that the specific heat
of the solution is the same as that for pure
water (4.184 J-mol-1C-1), and assume that the
mass of the final solution is 50.00 g.)
Calorimetry
The negative sign indicates that the reaction is
exothermic.
The value of H corresponds to the amount
of heat given off by the reaction of 1 mol of
HCl with 1 mol of NaOH (as indicated by the
reaction as written).
Calorimetry
How much of each reactant is present in this
experiment?
Calorimetry
So how many kJ of heat are given off by the
reaction of 0.002500 mol of each reactant?
Calorimetry
And by how much will that many kJ raise the
temperature of 50.00 grams of solution?
Recall that according to the first law of
thermodynamics, energy is conserved. So the
heat evolved (given off) by the reaction is
equal to the heat absorbed by the solution.
Calorimetry
Solving for T, we get 0.6673C.
That would make the final temperature, to the
appropriate number of significant figures,
22.67C.
Calorimetry
qsoln = m cp T
Calorimetry
Bomb
Calorimetry
Bomb calorimetry is used to determine the

energy change for a process that occurs at
constant volume.
Under constant-volume conditions, pressure is
not constant for a process that involves a net
production of gases, such as the combustion
of hydrocarbons and carbohydrates.
Bomb
Calorimetry
Hesss Law
Hess's law allows us to determine change in enthalpy
for a process that is made up of several steps
provided we know the enthalpy change associated
with each individual step.
A heat evolved in a given process can be expressed
as the sum of the heat of several processes that,
when added, yield the process of interest.
Useful to determine H of a reaction without
actually carrying out the reaction.
Hesss Law
Example: determining Hrxn for :
PH3(g) + F2(g) PF5(g) + H2(g)
Information available:
Hesss Law
In this example we added H values to
get H reaction.
Recall that the notation specifies
standard conditions of atmospheric
pressure and 25C.
Hess's law applies to all reactions,
whether or not they occur under
standard conditions.
Hesss Law
Enthalpies of reaction values for a great many
reactions have been determined and
tabulated.
Some H values are difficult or impossible to
determine directly.
In many cases Hess's law allows us to
determine the H of a reaction without
actually carrying out the reaction.
Hesss Law
Hesss Law
Formation of aluminum bromide

Nitrogen triiodide
Entalphies of
Formation
The enthalpy of formation is defined as the

enthalpy change for a process by which one
mole of a substance is formed from its
constituent elements, each in their standard
states.
The standard state for thermodynamics
(thermochemistry) is defined as 298 K and 1
atm pressure.
Entalphies of
Formation
Another way to determine the heat of

reaction without actually performing an
experiment
Hof (heat of formation): the change in
enthalpy that accompanies the formation of 1
mol of a substance from its elements, with all
substances in their standard states.
Entalphies of
Formation
Hof of the most stable form of any

element is zero.
Standard enthalpy change for any
reactions can be calculated when Hof
values for all reactants & products are
known.
Entalphies of
Formation
Entalphies of
Formation
Entalphies of
Formation
Using Hess's law allows us to determine H values

for reactions without actually performing them, as
long as we have sufficient data about the steps that
make up the reactions.
We do not always have all of the information
necessary to do this.
Fortunately, there is another way to determine the
heat of reaction without actually performing an
experiment.
Entalphies of
Formation
Hf ("standard delta H of formation"; also

called heat of formation) values are tabulated
for a large number of compounds. (Appendix
C in your textbook contains Hf values.)
H
f is defined as the heat of reaction for the
production of one mole of a substance from its
constituent elements, each in their standard
states.
Entalphies of
Formation
For instance, the Hf of liquid water is

the H for the following reaction (at 298
K).
Entalphies of
Formation
Entalphies of
Formation
Formation of water
Foods and Fuels

The concept of enthalpy of reaction is applied
to the metabolism of foods and the
combustion of fuels.
Most chemical reactions used for the
production of heat are combustion reaction.
The energy released when 1 g of a material is
combusted is often called fuel value.
Foods and Fuels

Because fuel values represent the heat
released in a combustion, fuel values are
positive number.
The fuel value of any food or fuel can be
measured by calorimetry.
Foods and Fuels

The reactions involved in producing energy
(combustion) from food & fossil fuels convert
carbon-based compounds to CO2 & H2O.
Food (proteins, carbohydrates, fats)
digestion glucose/blood sugar (C6H12O6)
C6H12O6(s) + 6O2(g) 6CO2(g) + 6H2O(l)
Ho = -2803 kJ
Foods and Fuels

Fuel value: the energy released when 1 g
of a substance was combusted.
The average fuel value of carbohydrates
is 17 kJ/g.
Fats produce CO2 & H2O in their
metabolism.
Foods and Fuels

The body put the chemical energy from
food to different uses:
To maintain body temperature
To drive muscles
To construct and repair tissues
Foods and Fuels

Any excess energy is stored as fats:
Fats are insoluble in water, which
permits their storage in the body
Fat produce more energy per gram
than either proteins or carbohydrates
(38 kJ/g)
Foods and Fuels
Foods and Fuels

During the complete combustion of
fuels:
Carbon is converted to CO2
Hydrogen is converted to H2O
The greater the percentage of carbon

and hydrogen in a fuel, the higher its
fuel value
Foods and Fuels
Foods and Fuels
Foods and Fuels
Foods and Fuels

Fossil fuels: Coal, Petroleum & Natural Gas.
Natural gas consists of gaseous hydrocarbons,
compound of hydrogen and carbon.
Petroleum is a liquid composed of hundreds of
compound mostly hydrocarbons, with
remainder being chiefly organic compounds
containing sulfur, oxygen or nitrogen.
Foods and Fuels

Coal,
which
is
solid,
contains
hydrocarbons of high MW as well as
compounds containing sulfur, oxygen, or
nitrogen.
Other energy sources: Nuclear energy
Nuclear energy is energy that is released
in the splitting or fusion of the nuclei of
atoms.
Foods and Fuels

22 % of electrical power in U.S.
7 % of total U.S. energy production.
Free of the polluting emissions that are a
major problem in the generation of energy
from fossil fuels.
Produce radioactive waste products
Foods and Fuels

Fossil fuel and nuclear energy are nonrenewable
sources of energy
Renewable energy, energy sources that are
essentially inexhaustible:
Solar energy from the sun

Wind energy
Geothermal energy
Hydroelectric energy
Biomass energy from crops (trees and corn) and from
biological waste matter.
Foods and Fuels

from food and those involved in the
combustion of fossil fuels are remarkably
similar.
Both ultimately convert carbon-based
compounds to carbon dioxide and water and
produce energy in the process.
Foods and Fuels

from food and those involved in the
combustion of fossil fuels are remarkably
similar.
Both ultimately convert carbon-based
compounds to carbon dioxide and water and
produce energy in the process.
An Introduction
to Entropy
Spontaneous process - a process that

proceeds on its own without any continuous
external influence.
Need either a release of energy or an increase in
disorder of the system.
An Introduction
to Entropy
Entropy - (S) - the amount of molecular

disorder or randomness in a system.
The larger the value of S, the greater the
molecular randomness.
S = Sfinal Sinitial.
An Introduction
to Entropy
Entropy - (S) - the amount of molecular

disorder or randomness in a system.
Sfinal > Sinitial
a. S is positive
b. system has become more random
Sfinal < Sinitial

a. S is negative
b. system has become less random
An Introduction
to Entropy
Spontaneous process.
Favored by decrease in H (negative H).
Favored by increase in S ( positive S).
An Introduction
to Free Energy
Gibbs free-energy change (G);

G = H - TS.
Sign of G used as a criterion for determining
spontaneity of a process.
G negative - spontaneous
G positive - nonspontaneous
An Introduction
to Free Energy
Temperature dependence (TS) term for G.

Spontaneity of some processes depends on
temperature.
Low temperatures - H dominates and controls
spontaneity.
High temperatures - TS dominates and controls
spontaneity.
An Introduction
to Free Energy
G = 0; process is at equilibrium.
Balanced
between
nonspontaneous.
spontaneous
H
T=
S
Entropy and Equilibrium
and
Thank You

Thermo Chemistry

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U N IVERSIT Y OF IN D ON ESIA

The Nature of Energy

Energy can be defined as the capacity

Matter possesses energy both

Thermochemistry is the study of the transfer of

The SI unit of energy is the joule.

Thus, the joule is a derived SI unit.

Calorie - the amount of energy necessary to raise the

The study of thermochemistry requires the definition

The system is the particular sample of matter under

The First Law of

Although kinetic energy can be converted

The First Law of

The First Law of

The First Law of

The ball of clay in Figure 6.1 possesses potential

The First Law of

As it falls, it has kinetic energy by virtue of its mass

The First Law of

Many forms of energy:

The First Law of

The First Law of

State functions are reversible.

The First Law of

The change in internal energy associated with a

q is heat transferred and w is work done.

The First Law of

The First Law of

Work the force (f) that produces the movement of

The First Law of

Expansion of the system.

The First Law of

Contraction of the system.

The First Law of

Calculate the amount of work done during a

The First Law of

Most of the material in this chapter is concerned

The relationship between internal energy and

Enthalpy, like internal energy, is a state function.

The enthalpy change of a reaction is equal in magnitude

B. Amount of heat transferred.

D. Reactions carried out at constant pressure.

Also known as the heat of reaction, the enthalpy of

Also known as the heat of reaction, the enthalpy of

H's can also be written for physical processes, and a

If the reactants in a chemical reaction have a greater

Hsolution, sometimes called heat of solution or

H heat of reaction Enthalpy of a system name given to the quantity E + PV.

The value of the enthalpy change H reported

Thermodynamic Standard State 298.15 K

Standard enthalpy of reaction an enthalpy

A detailed study of conversion factors found

Enthalpies of physical change.

Enthalpies of chemical change.

Ho values for a given equation.

A simple coffee-cup calorimeter

Bomb calorimetry is used to determine the

Formation of aluminum bromide

The enthalpy of formation is defined as the

Another way to determine the heat of

Hof of the most stable form of any

Using Hess's law allows us to determine H values

Hf ("standard delta H of formation"; also

For instance, the Hf of liquid water is