Thermochemistry

Notes prepared by Prof Dr Hikmat Al-Salim

What is thermochemistry?
It is a branch of thermodynamics that deals with the heat involved in chemical and physical change and specially with the concept of enthalpy H. H enthalpy means the heat involved at constant pressure

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Thermochemistry

Introduction
In order to observe and measure a change in energy, we must define the SYSTEM that

part of the universe that we are going to focus on.

Every thing else relevant to the change is defined as the SURROUNDINGS. Each particle in the system has potential and kinetic energy, and the sum of these energies for all the particles in the system is the INTERNAL ENERGY. Usually designated by the letter E or U. we shall use E.
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Thermochemistry
Thermochemistry is the study of the energy changes taking place during chemical reactions. Every substance contains stored chemical energy, called enthalpy, mainly by virtue of chemical bonds. Absolute enthalpy is hard to measure, but enthalpy changes during reactions are easy to measure because there will be an observable energy exchange between the chemicals and the surroundings.
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Specific heat capacity The heat needed to the temperature of 1 g of a substance by 1 C. Symbol: c, units: J/(gC). Heat capacity The heat needed to the temperature of an object by 1 C. Symbol: C (=c x m), units: J/C Heat of reaction The heat released during a chemical reaction. Symbol: none, units: J.
Molar heat of reaction The heat released during a chemical reaction per mole of reactant. Symbol: H, units: J/mol.
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Heat Calculations
To determine the amount of heat a substance produces or absorbs we often use q = mcT q: heat in J, c: specific heat capacity in J/(gC), m: mass in g, T: temperature change in C, This equation makes sense if you consider units Sample problem: (must know water = 4.18 J/gC) When 12 g of a food was burned in a calorimeter, the 100 mL of water in the calorimeter changed from 20C to 33C. Calculate the heat released.

q c.m.T 4.18 x 100 x 13 5.4 kJ

6

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Thermochemistry

More Questions
5 g of copper was heated from 20C to 80C. How much energy was used to heat the Cu? If a 3.1 g ring is heated using 10.0 J, its temp. rises by 17.9C. Calculate the specific heat capacity of the ring. Is the ring pure gold?

10.0 J c = q/mT= = 0.18 J/(gC) 3.1 g x 17.9C

The ring is not pure. Gold is 0.13 J/(gC)

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Thermochemistry

S = SPECIFIC HEAT C = HEAT CAPACITIES

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Thermochemistry

Enthalpy is a STATE FUNCTION

The path taken from reactants to products is irrelevant Thermochemical equations are chemical equations with an added heat term

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Thermochemistry

 The energy associated with a change such as: reactants products ( must return to starting T i.e as started with reactants) The internal energy E of this system has changed . To determine this change E we measure the difference between the systems internal energy after the change (E final) and before the change (E initial) : E = E final - E initial = E products E reactants Note that refer to the final state of the system MINUS the initial state. ALWAYS ONE FACT: The total energy of the system and surrounding is constant (conserved). This means that a change in the energy of the system is always accompanied by an opposite change in the energy of the surroundings.
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The energy of the system decreases E is negative in other words E final < E initial E < 0

The energy of the system increases E is positive which means: E final > E initial E > 0

The system is loosing energy to the surroundings

The system is gaining energy from the surroundings

Note that the change in energy is always a transfer of energy from system to surroundings, or vice versa
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Heat & Work

Energy transfer can appear in two forms; heat and work. Heat : (or thermal energy) usually given the letter q is the energy

energy transfer (mechanical, electrical, etc) involve some type of WORK (w). The total change in a systems internal energy is the sum of the energy transferred as heat and / or work. E = q + w ( value of q and w can be either negative

transferred between a system and its surroundings as a result of a difference in their temperatures only. All other forms of

or positive) We define the sign of the energy transfer from the systems perspective only. Energy coming into the system is positive Energy going out from the system is negative
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There are four simple cases: a-Two that involve only heat transfer b-Two that involve only work
1. Heat transfer as Heat only. For a system that does no work but transfers energy only as heat (q). i.e w = 0 therefore : E = q + w = q + 0 = q Case 1: Heat flowing out from a system. e.g. glass of hot water on the table. The water transfers energy as heat to the surroundings until the T of water equals that of surroundings. The systems energy decreases as heat flows out from the system, so the final energy of the system is less than its initial energy. Heat was lost by the system , therefore, q is negative

see next slide

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Thermochemistry

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Energy transfer as Heat only

q = negative Hot water, (the system, sys) transfers energy as heat (q) to the surroundungs (surr) until Tsys= Tsurr . Since Einitial > Efinal and
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E < 0

Case 2, Heat flowing into a system

E.g glass filled with ice-water. It gains energy as heat from the surroundings until the temperature of the water equals that of the surroundings. In this case energy is transferred into the system, so the final energy of the system is higher than its initial energy. Heat was gained by the system, so q is positive and E is positive
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Energy transfer as work only

E = q + w = 0 + w = w i.e The first case: work done by a system: In the reaction:

E =w

Zn( s ) 2H

aq

2Cl aq H 2 Zn2 aq 2Cl aq

We define the system as the atoms that make up substances. In the initial state, the systems internal energy is that of the atoms in the form of the reactants; metallic Zn and aqueous H+ and Cl- ions. In the final state, the systems internal energy is that of the same atoms in the form of the products, H2 gas and aqueosZn2+ and Cl- ions. As H2 is formed, some of the internal energy is used by the system to do work on the surroundings and push the piston outward.

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 The system is loosing energy as work is done. The internal energy of the system decreases as the reactants form products because the H2 gas does work (w) on the surroundings

by pushing back the piston. The reaction vessel is insulated, so q = 0 since Einitial > E final then E < 0 , and the sign of w is negative The H2 gas is doing pressure-volume work (PV work). This is a type of work in which a volume changes against an external pressure.
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Case 2 work done on a system

Consider the previous example in which if we increase the external pressure on the piston, the system gains energy because work is done on the system by the surroundings. Therefore w is positive

The sign convention q, w, and E

+ + 26-Nov-13

+ + -

+
Depend on sizes of q and w
Depend on sizes of q and w

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Summary of the sign conventions

E = q + w E is the change in internal energy of a system q is the heat exchange between the system and the surroundings w is the work done on (or by) the system w = -PV when a gas expands against a constant external pressure
Sign conventions for Work and Heat Process Work done by the system on the surroundings Work done by 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)
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Sign

(-) (+) (+) (-)

6.7

Units of energy
SI unit of energy is the joule (J). This is a derived unit composed of three basic units: 1 J = 1 kg.m2/s2 Both heat and work are expressed in joules. See how it applies to work. [ F=force , d = distance] Work = F x d . A force changes the velocity of (accelerates) a mass. Velocity has units of meters per second (m/s) so acceleration (a) has units of m/s2. Force therefore has of mass (m in kg) x acceleration F= m x a in units of kg.m/s2 Therefore w = F x d has units of (kg.m/s2) x m = kg.m2/s2 =J 1 cal = 4.184 J i.e 1J=1/4.184 = 0.2390 cal 1 kJ =1000J = 0.239 kcal = 239 cal
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Determining the change in internal energy

.e.g. when gasoline burns in car engine, the heat released causes
the products CO2 and H2O to expand, which pushes the pistons outward. Excess heat is removed by the cars cooling system. If the expanding gases do 451 J of work on the pistons and the system loses 325 J to the surroundings as heat, calculate the change in energy (E) in J, kJ and kcal. Solution: Calculating E from equation: E=

w+q

We have q= -324 J & w=-451 J E=-325J + (-451 J)=-776.1 J = -0.771 kJ To convert to calories we divide by 4.182 Therefore E=-0.776 kJ x (1 kcal/4.182 kJ) =

= -0.185 kcal
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What is State functions E

E is a state function , a property depends only on the current state of the system (its composition, volume, pressure, and temperature) not on the path the system took to reach that state. In fact the energy change of a system can occur by countless combinations of heat (q) and work (w). No matter what the combination, however, the same overall energy change occurs, because E does not depend on how the change takes place. Unlike w and q , they are not state functions because their values do depend on the path the system takes in undergoing the energy change. What this means is that changes in state functions E ,

P and V depend only on their initial and final states.

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Remember
Thermodynamics is the science of the relationship between heat and other forms of energy Thermochemistry is the science of the quantity of heat absorbed or evolved by chemical reactions. Types of energy: Kinetic energy Potential energy Chemical energy Heat energy Electric energy Radiant energy
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Energy
There are three broad concepts of energy: Kinetic energy is the energy associated with an object by virtue of its motion. Potential energy is the energy an object has by virtue of its position in a field of force. Internal energy is the sum of the kinetic and potential energies of the particles making up a substance.

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Heat of reaction
In chemical reactions, heat is often transferred from the system to its surroundings or vice versa. Heat flows from a region of higher temperature to one lower temperature . Once the temperature becomes equal, heat flow stops. Heat of reaction is the value of q required to return a system to the given temperature at the completion of reaction. Exothermic process Endothermic process
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Measuring H in the lab by bomb calorimetry

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Enthalpy (H): Heats of reaction and chemical change

The meaning of ENTHALPY. It determines energy changes at constant P To determine E we must measure both work (w)

and heat (q). The work done by an expanding gas is equal to P (external pressure - atmospheric) x V or (Vfinal - Vinitial)
P P W = -PV

Note that ( w) is negative because the work was done on the surroundings and the system loses energy

V
final state

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 But to determine W = -PV is not always possible, a thermodynamic variable called enthalpy eliminates the need to consider PV work separately. The enthalpy of a system is defined as the internal energy plus the product of the pressure and volume. H= E + PV the change in enthalpy H is then equal to the change in internal energy plus the product of the constant P and the change in the volume i.e H= E + PV

we can substitute for E i.e w+q

(w)=

- PV we get:

E=q + w= q+(- PV ) = q - PV At constant P , qp= E + PV = H

Thus the change in enthalpy equals the heat gained or lost at a constant pressure. With most changes occurring at constant P , H is more relevant than E , and easier to find; to find H measure qp.
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Exothermic and Endothermic Processes

Because E, P and V are state functions, H is also a state function which means that H depends on difference between H final and H initial . The enthalpy of a reaction , also called the heat of reaction , H reaction always refer to [ H final minus H initial ]. Or simply the difference

between enthalpies of products and reactants. Because the Hproducts can be either more or less than Hreactants , the sign of H reaction indicates whether heat

is absorbed or released in the change. We determine the sign of H by imagining the heat as a reactant or product.
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CH 4 ( gas ) O2 ( gas ) CO2 ( gas ) H 2 O( gas ) heat

Thermochemistry 29

 Because heat is released to the surroundings, the products (1 mol of CO2 and 2 mol of H2O ) must have less enthalpy than the reactants (1 mol CH4 and two mol of O2). Therefore, H = (Hproducts- Hreactants) is negative

CO2+2H2O
Enthalpy H

CH4+2O2
Enthalpy H

H final

H initial

H < 0

Heat out

H > 0

Heat in

CH4+2O2 CO2+2H2O H final Endothermic process Exothermic process

H initial

An exothermic (heat out) process releases heat to the surrounding and always is associated with a decrease in enthalpy of the system
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For exothermic processes :Hfinal < Thermochemistry

Hinitial30 and H < 0

 An endothermic (heat in) process absorbs heat and results in an increase in the enthalpy of the system. e.g. Heat + H2O(solid H2O(l) heat flows into the system from the surroundings. Notice heat appears as a reactant. Because heat is absorbed , the enthalpy of the liquid water is higher than that of solid water, therefore:
For endothermic processes :Hfinal > Hinitial and H > 0

Please note that the value of an enthalpy change refer to the reactants and products at the same

temperature.

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Remember

Sign conventions for Work and Heat Process Work done by the system on the surroundings Work done by 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)

Sign

(-) (+) (+) (-)

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Some Important Types Of Enthalpy Change

Some enthalpy changes are frequently studied and, therefore, they have special names: Heat of combustion Hcomb: When one mole of a substance combine with excess O2 in a combustion reaction Heat of formation Hf :when one mole of a compound is produced from its elements Heat of fusion Hfus: when one mole of a substance

melts

Heat of vaporization Hvap: Heat associated with vaporization of one mole of a substance.
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Stoichiometry of Thermochemical Equations

A thermochemical equation is a balanced equation that include the heat of reaction Hreaction . Keep in mind that the Hreaction shown refers to amounts (moles) of substances AND their states of matter in that specific equation. The enthalpy changes in any process has two aspects: 1-Sign the sign of H depends on whether the reaction is exothermic (-) or endothermic (+). Remember that a

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forward reaction has the opposite sign of the reverse reaction. 2H O2( g ) 2H 2O( g ) H 572 kJ 2( g ) 2H 2O( g ) 2H O2( g ) H 572 kJ 2( g )
Thermochemistry 34

2- Magnitude: the magnitude of H is proportional to the amount of substances reacting. Formation of 1 mole of water from its elements

Problem: The major source of Al in the world is bauxite ( mostly aluminium oxide). Its thermal decomposition can be represented by: Al2O3 (s) 2Al + O2 H =1676 kJ How many grams of Al can be produced from 1.000 x 103kJ. Solution: If 1676 kJ produced 2 x 26.98, then 1000 kJ will produce =(1000 x 26.98 x 2)/1676 = 32.20 gm of Al
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1 O2( g ) H 2O( g ) H 286 kJ 2( g ) 2

Ways of calculating (H)

There are three ways: 1. Measure it in the lab 2. Use Hesss Law 3. Use the enthalpies of formation

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Hesss law of heat summation.

Many reactions are difficult or impossible to carry out in the labs in order to measure their enthalpies. Yet it is possible to calculate their enthalpies. One of the most powerful applications of the State Function property of the enthalpy allows us to find H of any reaction for which we can write an equation, even if it is impossible to carry out. The application is based on Hesss law of heat

summation: the enthalpy change of an overall process is the sum of the enthalpy changes of its individual steps. Let us see how we apply this law e.g. in the case the oxidation of sulphur trioxide.
Thermochemistry 37

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Hesss Law
For any chemical change made in several steps, the net H is equal to the sum of the H values of the separate steps

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 When we burn S in an excess of O2 , SO2 is formed, not SO3

equation 1 S ( s ) O2( g ) SO2( g )

H1 296 .8 kJ H 3 ?

equation 2 2SO2( g ) O2( g ) 2SO3( g ) H 2 198 .4 kJ equation 3 S ( s ) 3 / 2O2( g ) SO3( g )

Hesss law tells us that if we manipulate equation 1 and / or 2 so that they add up to eq 3, then H3 is the sum of the manipulated H values of equation 1 & 2.

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equation 1 S ( s ) O2( g ) SO2( g )

H1 296.8 kJ

1 (equation 2 2SO2 ( g ) O2( g ) 2SO3( g ) H 2 198.4 kJ ) 2 1 1 SO2( g ) O2( g ) SO3( g ) H 2 99.2kJ 2 2 _______________________________________________ 1 equation 3 S ( s ) O2( g ) SO2( g ) O2( g ) SO2( g ) SO3 H 3 ? 2 adding the H we get : 1 H 3 H1 H 2 296.8 kJ (99.2 kJ ) 396.0 kJ 2
Once again the key point is that H
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is a state function
40

Another example
e.g. find H for the reaction: 2 CH4(g) + 3 O2(g) 2 CO(g) + 4 H2O(l) using the following data:
CH4(g) + 2 O2(g) 2 CO(g) + O2(g) CO2(g) + 2 H2O(l) H = -890 kJ 2 CO2(g) H = -566 kJ
.(1)

(2)

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Thermochemistry

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Continue
Multiply equation (1) by 2 , and reaction (2) by -1 we get: 2 CH4(g) + 3 O2(g)
2 CH4(g) + 4 O2(g) 2 CO2(g) + 4 H2O(l) after multiplication H = -1780 kJ 2 CO2(g) 2 CO(g) + O2(g) H = +566 kJ after multiplication by -1 2 CH4(g) + 3 O2(g) 2 CO(g) + 4 H2O(l) H = -1214 kJ

2 CO(g) + 4 H2O(l)

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Formation equations and their enthalpy changes

In a formation equation, 1 mole of a compound forms from its elements. Standard heat of formation : H o is the enthalpy change for the f formation equation when all the substances are in their standard states . e.g. for methane: C 2H CH H o 74.9 kJ
( graphite ) 2( g ) 4( g ) f

Other examples:

1 Na( s ) Cl2( g ) NaCl H o f 411.1 kJ 2 1 C( graphite ) 3H 2( g ) O2( g ) C2 H 5 OH (l ) H o f 277.6 kJ 2

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Rules in calculating standard heat of formation

1. An element in its standard state is assigned H f =0 Note in the o past examples we regardedH f for Na = 0 2. The standard state of diatomic gases is X2 and not X 3. Most compounds have a negative heat of formation.
o

Standard Heats of Formation Formula Ca CaO Cl2 HCl S8 rhombic S8 monoclinic

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H o f
0 -635.1 0 -92.3 0 0.3 143 ( note it is positive)
Thermochemistry 44

O3

Calculating Bond Energies & Enthalpies

Problem Estimate the change in enthalpy, H, for the following reaction: H2 (g) + Cl2 (g) 2 HCl (g) Solution To work this problem, think of the reaction in terms of simple steps: Step 1 The reactant molecules, H2 and Cl2, break down into their atoms H2(g) 2 H(g) Cl2(g) 2 Cl(g)
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 Step 2 These atoms combine to form HCl molecules 2 H (g) + 2 Cl (g) 2 HCl (g) In the first step, the H-H and Cl-Cl bonds are broken. In both cases, one mole of bonds is broken. When we look up the single bond energies for the H-H and Cl-Cl bonds, we find them to be +436 kJ/mol and + 243 kJ/mol, therefore for the first step of the reaction: H1 = +(436 kJ + 243 kJ) = +679 kJ Bond breaking requires energy, so we expect the value for H to be positive for this step. In the second step of the reaction, two moles of H-Cl bonds are formed. Bond breaking liberates energy, so we expect the H for this portion of the reaction to have a negative value. Using the table, the single bond energy for one mole of H-Cl bonds is found to be 431 kJ: 46 26-Nov-13 H2 = -2(431 kJ) Thermochemistry = -862 kJ

 By applying Hess's Law, H = H1 + H2 H = +679 kJ - 862 kJ H = -183 kJ Answer The enthalpy change for the reaction will be H = -183 kJ.

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Assignments
1) Calculate H for the reaction: C2H4 (g) + H2 (g) C2H6 (g), from the following data. C2H4 (g) + 3 O2 (g) 2 CO2 (g) + 2 H2O (l) H = -1411. kJ C2H6 (g) + 3 O2 (g) 2 CO2 (g) + 3 H2O (l) H = -1560. kJ H2 (g) + O2 (g) H2O (l) H = -285.8 kJ 2) Find H for the reaction 2H2(g) + 2C(s) + O2(g) the following thermochemical data. C2H5OH (l) + 2 O2 (g) 2 CO2 (g) + 2 H2O (l) C (s) + O2 (g) CO2 (g) H2 (g) + O2 (g) H2O (l)
26-Nov-13 Thermochemistry

C2H5OH(l), using H = -875. kJ H = -394.51 kJ H = -285.8 kJ

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3) Find the H for the reaction below, given the following reactions and subsequent H values: PCl5(g) PCl3(g) + Cl2(g) P4(s) + 6Cl2(g) 4PCl3(g) H = -2439 kJ 4PCl5(g) P4(s) + 10Cl 2(g) H = 3438 kJ answer = 249.8 kJ 4) Find the H for the reaction below, given the following reactions and subsequent H values: H2SO4(l) SO3(g) + H2O(g) H2S(g) + 2O2(g) H2SO4(l) H = -235.5 kJ H2S(g) + 2O2(g) SO3(g) + H2O(l) H = -207 kJ H2O(l) H2O(g) H = 44 kJ answer = 72 kJ
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5) Find the H for the reaction below, given the following reactions and subsequent H values: CO2(g) C(s) + O2(g) H2O(l) H2(g) + 1/2O2(g) H = 643 kJ C2H6(g) 2C(s) + 3H 2(g) H = 190.6 kJ 2CO2(g) + 3H2O(l) C 2H6(g) + 7/2O2(g) H = 3511.1 kJ answer = 886 kJ

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