THERMODYNAMICS

THERMOCHEMISTRY

• The study of energy or heat flow

that accompanies a chemical
reaction and/or physical
transformations
HEAT (q)
• is the form of energy
transfer between two
objects as a result of
their difference in
temperature .
• Energy generally flows
from a hotter object to
a cooler one until
thermal equilibrium is
reached.
TEMPERATURE

• A property of matter
that determines whether
there can be heat
energy transfer from one
object to another.
CONCEPT OF HEAT
SYSTEM is the part of the
universe being studied or
to which attention is
focused.
SURROUNDINGS include
everything else in the
universe.
Open System, Closed System, Isolated System
EXOTHERMIC AND ENDOTHERMIC
ENDOTHERMIC REACTION
happens if the system
absorbs heat from the
surroundings.

EXOTHERMIC REACTION
happens when heat flows
from a system to its
surrounding
 Sample Problem
Identify whether the following processes are endothermic or exothermic:
1. Burning of Coal
Exothermic Reaction

2. Explosion of a firecracker triggered by a spark

Exothermic Reaction

3. Solid lead (II) chloride (PbCl2) dissolves only in hot water

Endothermic Reaction
FIRST LAW OF THERMODYNAMICS
• According to the law of conservation of energy, energy can neither be created nor
destroyed. It can only be transferred between the system and the surroundings.
• The energy of the system ( Esys ) and the energy of its surroundings ( Esurr ) are
related by the following equation.
FIRST LAW OF THERMODYNAMICS

Esys = - Esurr The negative sign indicates the flow of energy. As the system releases
energy, the surroundings absorb it. Whatever amount of energy that is lost
by the surroundings must be gained by the system

Esys = q + w The law implies that the net energy flow to or from any system comes in
the form of either work or heat. When work is done on the system, it gains
energy and work is denoted as positive (+w). When the system does the
work, it uses up or transfers some of its energy so that work is denoted as
negative (-w)
Moreover, the system may also absorb heat for which q is positive (+q) ,
or it may release heat to the surroundings for which q is negative (-q) .
Thus, the net change in energy can either be positive or negative
depending on the means and direction of the energy transfer involved.
 Sample Problem
Calculate the change in energy for the following processes. Identify if the process is endothermic or exothermic

1. A gas releases 35 J of heat as 84 J of work was done to compress it.

Given: q = 35 J
w = 84 J
RTF: Change in energy
Solution: Esys = (-q) + (+w)
Esys = (-35 J) + (84J)
Final Answer: 49J (Endothermic Process)
 Sample Problem
Calculate the change in energy for the following processes. Identify if the process is endothermic or exothermic

2. A gas absorbs 48 J of heat as it does 72 J of work by expanding

Given: q = 48 J
w = 72 J
RTF: Change in energy
Solution: Esys = (+q) + (-w)
Esys = (48 J) + (-72 J)
Final Answer: -24 J (Exothermic Process)
 Assignment

1. What is the work done by a system when it absorbs 47.0 J of heat and gain
12.0 J of energy?
2. How much heat is released by the system when 45 J of work is done on it to
decrease its energy to 23 J?
 ANSWERS:

1. What is the work done by a system when it absorbs 47.0 J of heat and gain
12.0 J of energy?
Given: q = 47.0 J
Esys = 12.0 J
RTF: w
Solution: Esys = (q) + (w)
12.0 J = (47.0 J) + (-w)
w= (47.0 J ) + (-12.0 J)
Final Answer: w = (-)35 .0J
 ANSWERS:

2. How much heat is released by the system when 45 J of work is done on it to

decrease its energy to 23 J?
Given: w = 45 J
Esys = 23 J
RTF: q
Solution: Esys = (q) + (w)
23J = (-q) + (45 J)
(23J) + (-45J) = (-q)
Final Answer: (-)q = - 22 J
 Calorimetry
• The measure of the flow of energy (as heat) between the system and its
surroundings
• The amount of heat absorbed by the system is a function of its change in
temperature.
q=C t
t = tfinal – tinitial
From the equation, heat and temperature change are related by a proportionality
constant referred to as heat capacity (C) , which is the amount of energy needed to
increase the temperature of a substance or material by 1º C. The heat capacity of the
substance can only be determined experimentally through calorimetry. For a pure
substance, the heat capacity is equal to the product of its mass (m) and specific heat (c)
C = mc
 Calorimetry
Therefore , Table 3-1 Specific Heat of Common Pure Substances
q = mc t Substance Specific Heat (J/g.ºC)

The specific heat of the substance H2O(s) , ice 2.11

is the amount of energy needed to H2O(l) 4.18
increase the temperature of one H2O(g) , steam 2.08
gram of the substance by 1ºC. The
CO2(g) 0.843
specific heat of a substance is
constant. Different physical states Cu(s) 0.385
of the same substance have Al(s) 0.897
different values of specific heat. Fe(s) 0.450
C2H5OH(l) 2.43
 Calorimeter
• An insulator apparatus that contains water or
any liquid of known heat capacity.
• In calorimetry, the system of interest can be a
substance (for which heat of solution or heat of
dissociation is measured) or a chemical reaction
(for which heat of reaction or heat of
neutralization is measured)
• The system exchanges heat with the water and
the components of the calorimeter.
• This heat exchange can be mathematically
expressed as
qsys = - [ q calorimeter + q water ]
 Calorimeter
• In some cases, the calorimeter is an
excellent insulator and absorbs only a
negligible amount of heat.
• Thus, the system is assumed to exchange
heat only with the water in the
calorimeter and the equation is simplified
to
qsys = -q water = -( mc t)water ]
 Sample Problem
1. How much heat is absorbed by liquid water that weighs 550.0 grams as it is
heated from 25.0ºC to 95.0ºC?
Given: mass = 550.0 grams
tinitial = 25.0 ºC
tfinal = 95.0ºC
RTF: heat absorbed
Solution: q = mc t
q = (550.0 g )(4.18J/g.ºC)(95.0ºC - 25.0ºC)
Final Answer: q = 1.61 x10 5 J or 161 kJ
 Sample Problem
2. How much heat is released by a 76.0 gram piece of copper as it cools from
450.0ºC to 28.0 ºC?
Given: mass = 76.0 grams
tinitial = 450.0 ºC
tfinal = 28.0ºC
RTF: heat absorbed
Solution: q = mc t
q = (76.0 g )(0.385J/g.ºC)(28.0ºC - 450.0ºC)
Final Answer: q = -1.23 x10 4 J or -1.23x10 kJ
 ENTHALPY OF A CHEMICAL REACTION:
THERMOCHEMICAL EQUATION
• A chemical equation that shows the value and direction of heat involved in a reaction
is specifically called thermochemical equation.
• The amount of heat absorbed or released by a chemical reaction at constant
atmospheric pressure is called enthalpy (H).
• The difference between the enthalpy of the products and the reactants is called
enthalpy of reaction ( H).
H = Hproducts – Hreactants
• The standard molar enthalpy of formation( Hºf ) of a compound is the change in
enthalpy when the compound is formed from its elements under standard conditions
(1 atm, 25º C)
• The standard enthalpy of a reaction ( Hºrxn) can thus be calculated by subtracting
the sum of the enthalpies of formation of the products and the sum of the enthalpies
of formation of the reactants.
ENTHALPY OF A CHEMICAL REACTION:
THERMOCHEMICAL EQUATION
Consider the hypothetical equation
aA + bB cC + dD
Where a, b, c, and d are the respective coefficients of the substances A, B, C, D in the
balanced chemical equation. The sum of the enthalpies of formation of the products is
calculated as :
∑ Hºf (products) = c Hºf (C) + d Hºf (D)
And for reactants
∑ Hºf (reactants) = a Hºf (A) + b Hºf (B)
Then, the standard molar enthalpy of the hypothetical reaction is calculated as
Hºrxn = ∑ Hºf (products) - ∑ Hºf (reactants)
ENTHALPY OF A CHEMICAL REACTION:
THERMOCHEMICAL EQUATION
Table 3-2
Hºf of Some Common Substances
Substance Specific Heat Substance Specific Heat
Hºf(kJ/mol) Hºf(kJ/mol)
C (graphite) 0 H2O(l) -285.8
CO (g) -110.5 N2 (g) 0
CO2(g) -393.5 NaCl -411.2
C2H5OH(l) -277.7 NH3(g) -46.3
CaCO3(s) -1206.9 NO(g) 90.29
CaO(s) -635.6 NO2(g) 33.85
Fe2O3(s) -824.2 N2O (g) 81.56
H2O(g) -241.8 O2(g) 0
 ENTHALPY OF A CHEMICAL REACTION:
THERMOCHEMICAL EQUATION
If a reaction is an overall process that can be attained through a series of steps of reactions,
then the enthalpy of this overall reaction can be calculated from the thermochemical equations
defining the reactions leading to it. This approach can be summarize using Hess’s Law , which
states that the enthalpy of a sum of a series of reactions is equal to the sum of the enthalpies of
those two reactions. In such cases, the following rules must be applied:

Rule 1: Enthalpy is an extensive property; it depends on the amount of reactants and products
Rule 2: The H for a forward reaction is equal in magnitude but opposite in sign to its reverse
reaction.
Rule 3: The H for a reaction is the same whether it occurs in one step or in a series of steps.
 SAMPLE PROBLEM

1. Using the standard molar enthalpies of formation given, calculate the standard
enthalpy of reaction for the combustion of propane (C3H8) into carbon dioxide
and water.
C3H8(g) + 5 O2(g) 3CO2(g) + 4 H2O(g)
Substance C3H8(g) O2(g) CO2(g) H2O(g)
Hºf (kJ/mol) -104.00 0 -393.5 -241.8
RTF: Standard Enthalpy Hºrxn
Solution: ∑ Hºrxn = [3 Hºf (CO2,g) + 4 Hºf (H2O,g)] – [ Hºf(C3H8, g) + 5 Hºf (O2g)]
∑ Hºrxn = [3 (-393.5kJ) + 4(-241.8kJ)] – [ (-104.00kJ)+ 5(0)]
Final Answer: ∑ Hºrxn = -2044 kJ
 SAMPLE PROBLEM

2. The thermochemical equation for the incomplete combustion of carbon monoxide is

represented as
2C(s) + O2(g) 2CO(g)
Compute for the H of the reaction if the overall process above can occur in two steps
whose thermochemical equations are given below:
(1) C(s) + O2(g) CO2(g) H = -393.5 kJ
(2) 2CO(g) + O2(g) 2CO2 H= -566.0 kJ
RTF: Enthalpy of Reaction ( H)
Solution:
Rule 1: Equation needs to be multiplied by 2 since the C(s) in the overall
equation has a coefficient of 2.
[ C(s) + O2(g) CO2(g) H = -393.5 kJ ] x2
 SAMPLE PROBLEM

Solution:
Rule 1: Equation needs to be multiplied by 2 since the C(s) in the overall
equation has a coefficient of 2.
[ C(s) + O2(g) CO2(g) H = -393.5 kJ ] x2
2C(s) + 2O2(g) 2CO2(g) H = -787.0kJ
Rule 2: equation must be reversed since carbon monoxide is in the products side
of the desired chemical equation.
2CO(g) + O2(g) 2CO2 H= -566.0 kJ
2CO2(g) 2CO(g) + O2(g) H = 566.0 kJ
 SAMPLE PROBLEM

Solution:
Rule 3: By Hess’s Law, the H of the overall reaction can be calculated from the
H of the two (manipulated) reactions leading to it. In summary,
2C(s) + 2O2(g) 2CO2(g) H = -787.0kJ
2CO2(g) 2CO(g) + O2(g) H = 566.0 kJ
2 C(s) + O2(g) 2 CO(g) H = -221.0 kJ