Chapter 5 Thermochemistry

Energy
Unlike matter, energy is known and recognized by its effects. It cannot be seen, touched, smelled, or weighed. Energy is defined at the capacity to do work OR to transfer heat. Physical and chemical changes are always accompanied by energy changes. Energy changes will occur between a system and its surroundings. A system is that piece of the universe that you wish to study. Everything else is the surroundings.

 The heat of the system, q, will be + if it is an endothermic reaction and if it is an exothermic reaction. The work, w, will be + when work is done on the system by the surroundings and it will be if work is done on the surroundings by the system. (work is similar to heat, if the system takes in the work from the surroundings, then work will be entering the system and w = +. If the system creates work, then work will be exiting the system and w = -.)

The internal energy of a system: Esys = q + w

Work (a part of the internal energy of a system E= q + w)

w=Fxd (F = mass x acceleration) In chemistry, an example of mechanical work is the expansion of a gas. As the gas expands, it will push a piston upwards against the external atmospheric pressure.

Types of Energy
Radiant energy- solar energy that comes from the sun. Thermal energy- the energy associated with the random motion of atoms and molecules. Chemical energy- energy that is stored within the structural units of chemical substances. Potential energy- energy available by virtue of an objects position. Kinetic energy- the energy produced by a moving object.

Energy Transfer
Heat is the most common form of energy change.
Thermal energy is related to the total amount of molecules in random motion. Heat is the transfer of thermal energy between two bodies that are at different temperatures, which is represented by the lower case letter, q = heat.

Energy will transfer from matter at a higher temperature to matter at a lower temperature.
Thermal energy will continue to transfer until the temperature of both forms of matter are equal.

Measurements of Energy
To measure energy changes, we usually use the unit joule (J). The joule is an SI derived unit.

Another way to measure energy changes is the calorie (cal), which we are much more familiar with because our food is measured in kilocalories with an uppercase (Cal) symbol.
1 cal = 4.184 joules. 1 Cal = 1000 cal.

Caloric values are the amount of energy the human body can obtain by chemically breaking down food.

Energy and Chemical Changes

Chemical changes are always associated with a change in energy.
Thermochemistry is the study of heat change in chemical reactions.
Endothermic Reactions - If energy is absorbed in a reaction, the reaction is endothermic. When this happens, energy will be pulled from the surroundings into the reaction in order to form products. No heat, light or motion will be given off in the reaction, instead the reaction will turn cold because it will pull energy out of the surroundings in order to form the product.

Reactant A + Reactant B + Energy

Products

I remember endothermic because energy is entering the reaction but it is not leaving.

Exothermic Reactions
If energy is given off by a reaction, the reaction is exothermic. When this happens, energy will be given off by the system into the surroundings. Heat, motion or light will be given off in the reaction. Reactant A + Reactant B Products + Energy

I remember exothermic because energy is exiting the reaction and leaving the system into the surroundings.

Exothermic Reaction

Endothermic Reaction

Activation Energy Both endo and exothermic reactions require a minimum amount of energy in order to start a reaction. This is called the activation energy. If we do not have activation energy, the bonds between the reactants will never break and a reaction will never occur.

Enthalpy
Almost every reaction that we see will take place at constant pressure. Beakers being open in the lab, etc. The pressure is usually equally to the atmospheric pressure of 1 atm. Enthalpy (H) - is the heat flow into or out of a system in a constantpressure process. (Meaning the heat flow that we normally experience inside a lab with open beakers.) Remember that heat is defined as the transfer of thermal energy between two bodies at different temperatures. Thermal energy is the energy associated with the random motion of atoms and molecules. Enthalpy can therefore also be thought of as the transfer of energy, into or out of a system, that is associated with the random motion of atoms and molecules at a constant-pressure process.

The Enthalpy of Reaction

Because enthalpy is the transfer of energy as heat flow into or out of a system, it is impossible to determine the enthalpy, H, of a substance. For this reason, we measure the enthalpy of reaction, H. This is the difference between the enthalpies (heat flow) of the products and the enthalpies (heat flow) of the reactants: H = H (products) H (reactants) H represents the heat given off or absorbed during a reaction. This can be a + or value. For endothermic reactions, heat is absorbed by the system from the surroundings and it is therefore a + H value. For exothermic reactions, heat is released by the system into the surroundings and it is therefore a - H value.

High

Higher thermal energy = Higher movement

of molecules

H2O(s)

H2O(l)

Lower thermal energy = Lower movement

Low

of molecules

High

Higher thermal energy = Higher movement of molecules

CH4(g) + 2O2(g) CO2(g) + 2H2O(l)

Low

Lower thermal energy = Lower movement of molecules

Thermochemical Equations
The previous two examples would have the following thermochemical equations:
H2O(s) H2O(l) H = + 6.01kJ CH4(g) + 2O2(g) CO2(g) + 2H2O(l) H = -890.4 kJ What would happen to the enthalpy if the combustion of methane went straight into making a gaseous water form for a product? CH4(g) + 2O2(g) CO2(g) + 2H2O(g) H = -802.4 kJ This shows us the value of knowing the term thermal energy and how it relates to enthalpy and it also shows us that writing the physical states of each reactant and product is necessary in a thermochemical equation.

Thermochemical equations
The stoichiometric coefficients always refer to the number of moles of a substance. H2O(s) H2O(l) H = + 6.01kJ Therefore, the equation for the melting of ice may be read as follows: one mole of liquid water is formed from one mole of ice at 0 degrees Celsius, the enthalpy change is 6.01 kJ. CH4(g) + 2O2(g) CO2(g) + 2H2O(l) H = -890.4 kJ For the combustion of methane, we interpret the equation this way: when 1 mole of gaseous methane reacts with 2 moles of gaseous oxygen to form 1 mole of gaseous carbon dioxide and 2 moles of liquid water, the enthalpy change is -890.4 kJ.

Thermochemical Equations
When we reverse an equation, we change the roles of reactants and products. Therefore, the sign of the H is changed, but its numerical value remains the same. For example if we reversed the previous equation of the ice melting, to freezing, the equations would change like the following:

H2O(s) H2O(l)

H2O(l) H2O(s)

H = + 6.01kJ H = - 6.01kJ

If we multiply both sides of a thermochemical equation by a factor of n, then H must also change by a factor of n. Therefore if the above ice melting is changed by a factor of 2 = n, the following occurs: 2H2O(s) 2H2O(l) H = + 2(6.01kJ) = + 12.0 kJ

Thermochemical Equation Example Problem

Given the thermochemical equation SO2(g) + O2(g) SO3(g) H = -99.1 kJ Calculate the heat evolved when 74.6 g of SO2 (molar mass = 64.07 g/mol) is converted to SO3. 74.6 g SO2 1 mol SO2 -99.1 kJ = -115 kJ 64.07 g SO2 1 mol SO2

Another example: Calculate the heat evolved when 266 g of white phosphorus (P4) burn in air according to the equation: P4(s) + 5O2(g) P4O10(s) H = -3013 kJ

Thermochemical Equation Example Problem

Pentaborane-9, B5H9, is a colorless, highly reactive liquid that will burst into flame or even explode when exposed to oxygen. The rxn is:
2 B5H9(l) + 12O2(g) 5B2O3(s) + 9H2O(l) H = -9036.6 kJ

Calculate the heat released from the reaction if 100 g of B5H9 react with oxygen.
100 g B5H9 1 mol B5H9 -9036.6 kJ = -7158.3 kJ 63.12 g B5H9 2 mol B5H9

Specific Heat / Heat Capacity

The heat needed to raise the temperature of one gram of a substance by one Celsius degree is called the specific heat (s) = J/g oC.

Every substance has its own specific heat. For example, the heat required to raise the temperature of one gram of liquid water one Celsius degree is 4.184 joules.
Specific heat (s) of water for different phases:
Solid H2O = 2.09 J/goC Liquid H2O = 4.184 J/goC Gas H2O = 2.01 J/goC

Memorize This!

s = 4.184 J/g . Co for liquid water

And s = 1 cal/g . Co for water.

When the amount of a substance is given, its heat capacity (C), is the amount of heat that is required to raise that given quantity one degree Celsius. C = mass x specific heat = J/oC

Measuring Energy Changes

A calorimeter is a device used to measure the energy given off or absorbed during chemical or physical changes.
When the reaction occurs inside the sample cup, it causes a change in temperature of the water. The temperature change is used to measure the heat absorbed or released by the reaction.

The law of conservation of energy

The law of conservation of energy says that in an enclosed system, energy will be conserved. From this law, we can see how a calorimeter works to measure energy. The energy that is released from the reaction is transferred into a change in temperature (thermal energy).

From this law, the following relationship is used to calculate the heat that is gained or lost by a reaction inside a calorimeter.
(heat gained or lost by water) = (mass in grams) x ( change in temperature) x (specific heat)

q = (m) x ( Tfinal Tinitial) x (s) This is also the same as: q = C x (Tfinal Tinitial)

Constant-Pressure Calorimetry
Remember that the enthalpy of a rxn H, must deal with the heat transfer of a rxn that occurs at constant pressure. What happens if we use a calorimeter at constant pressure? A constant pressure calorimeter will mean that the qrxn will equal the enthalpy of a rxn H. This is because it is the transfer of heat for the rxn at constant pressure.

Constant-Pressure Calorimetry
The pressure of the system is always constant, therefore the calorimeter is called a constant-pressure calorimeter. The heat released or absorbed by the reaction will raise or lower the temperature of the surrounding water. From this we can calculate the heat gained or lost from the reaction. Because the calorimeter is well insulated, we assume that no heat is lost to the surroundings (this is called an adiabatic system). Therefore we can consider the calorimeter an adiabatic/isolated system and we can write: qsystem = qsoln + qcalorimeter + qrxn qsystem = 0 (no heat enters or leaves an adiabatic/isolated system) qrxn = -(qsoln + qcalorimeter) qsoln can be found from: qsoln = msoln (specific heat (s) of soln) ( T) We find the qcalorimeter by measuring a substance of known qrxn and then we rearrange the equation to find the qcalorimeter.

Standard Enthalpy of Formation

Up to this point we know that we can determine the enthalpy change of a rxn H, by measuring the heat that is absorbed or released by the rxn (at constant pressure). And from the following equation: H = H (products) H (reactants) We can see that if we knew the actual enthalpies, H, of the products and the reactants than we could calculate the H. But, remember that we do not know the actual enthalpy of a substance, H. Only values of H that are relative to a determined reference point can be determined. This is a problem that scientists had with the being able to express the elevations of mountains or valleys. How do you express the starting point of elevation? You dont do it from the center of the earth. Scientists use the sea level as being the elevation of zero meters or feet. In the same way, chemists agreed on a starting point for enthalpy, H.

Standard Enthalpy of Formation

The sea level reference point for all enthalpy expressions is called the standard enthalpy of formation ( Hfo), which is defined as the heat change that results when one mole of a compound is formed from its elements at a pressure of 1 atm. Elements are said to be in the standard state at 1 atm, therefore we use the term standard enthalpy. The superscript of o represents standard-state conditions (1atm), and the subscript f stands for formation. (the standard enthalpy of formation is usually measured at 25 degrees Celsius even though it is not stated). Tables of the standard enthalpy of formation exist for elements and compounds. The units associated with ( Hfo), are typically measured in (kJ/mol). By convention, the standard enthalpy of formation of any element in its most stable form is zero. For example, oxygen exists as ozone (O3), at 1 atm and 25oC and also as molecular oxygen (O2). But its most stable form is (O2), therefore Hfo = 0 for O2.

Standard Enthalpy of Reaction

Once we know the values of the standard enthalpies of formation ( Hfo), we can calculate the standard enthalpy of reaction, ( Hrxno), which is the enthalpy of a reaction carried out at 1 atm. For example, consider the following rxn: aA + bB cC + dD Where a, b, c and d are the stoichiometric coefficients. For this rxn ( Hrxno), is given by:
Hrxno = [c Hfo(C) + d Hfo(D)] [a Hfo(A) + b Hfo(B)] We generalize the above eqn as: Hrxno = n Hfo (products) m Hfo (reactants) Where n and m are the stoichiometric coefficients (in moles) for the reactant and product and (sigma) means sum of.

Standard Enthalpy of Reaction

In order to calculate the Hrxno, like in the previous slide, we must know the Hfo values for the compounds participate in the reaction. There are two different ways to find the standard enthalpy of formation ( Hfo): 1) The Direct Method. 2) The Indirect Method. 1) The direct method is used for compounds that can be synthesized from their elements. For example, if we want to know the enthalpy of formation of carbon dioxide, we must measure the enthalpy of the rxn when carbon (graphite) and molecular oxygen in their standard states are converted to carbon dioxide in its standard state: C(graphite) + O2(g) CO2(g) Hrxno = -393.5 kJ

Hrxno = n Hfo (products) m Hfo (reactants) Hrxno = (1mol) Hfo (CO2(g)) [(1mol) Hfo (C,graphite) + (1mol) Hfo (O2(g))] = -393.5 kJ
Because O2 and C are both stable forms their Hfo = 0. Therefore Hfo (CO2(g)) = - 393.5 kJ/mol

Hesss Law
2) The indirect method is used for compounds that can not be
synthesized from their elements. For this case, Hfo, can be determined by an indirect method called Hesss Law When reactants are converted to products, the change in enthalpy is the same whether the rxn takes place in one step or in a series of steps. In other words, if we can break down the rxn of interest into a series of rxns for which the Hrxno can be measured, we can calculate the Hrxno for the overall rxn. This is known as the law of heat summation. Example: if you want to know the standard enthalpy of formation of methane (CH4), we would represent the rxn from its standard states like: C(graphite) + 2H2(g) CH4(g) But, this rxn does not take place as written above, so we cannot measure the enthalpy change directly. Instead we must find an alternative route using Hesss Law.

Hesss Law
C(graphite) + 2H2(g) CH4(g) We must use the indirect route of Hesss Law in order to find the Hrxno for the above equation. The following rxns have been studied and the Hrxno values are known to be as follows: (a) C(graphite) + O2(g) CO2(g) Hrxno = -393.5 kJ (b) 2H2(g) + O2(g) 2H2O(l) Hrxno = -571.6 kJ (c) CH4(g) + 2O2(g) CO2(g) + 2H2O(l) Hrxno = -890.4 kJ Hesss Law basically says to sum the above reactions in any way possible in order to get the final overall rxn to look like the reaction that you need to find the Hrxno for. This may mean that you will have to multiply some of the above rxns in order to cancel unwanted elements on each side of the rxn OR it might mean that you will have to reverse a rxn (dont forget to change the sign of the Hrxno). Lets figure it out!

Thermodynamics
Thermochemistry is part of a larger subject called Thermodynamics, which is the scientific study of the interconversion of heat and other kinds of energy. We will concentrate more heavily in later chapters on this subject. In thermodynamics, we study changes in the state of a system, which is found by the properties such as composition, energy, temperature, pressure and volume. A State Function is a property that is determined by the state of the system no matter how that condition was achieved. This means that the state of the system depends only on the final and initial states of the system and not on how those positions were accomplished. State functions are represented with capital letters. Some examples are: E, P, V, and T. You can find any of the state functions values by: Final - Initial

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In a State Function, the state of the system depends only on the final and initial states of the system and not on how those positions were accomplished. Such as: E, P, V and T

The First Law of Thermodynamics

If you had to take a guess about what law the first law of thermodynamics is, and I told you that it has to deal with energy, what do you think it would be? First Law of Thermodynamics Energy is never created or destroyed, it is only converted from one form to another (law of conservation of energy). Therefore: E = Efinal Einitial Which we know already because it is also a state function. (For example, we might not know the internal energy of the products or the reactants, but we can measure the change in energy of both from the above equation.) The internal energy of a system is composed of two components: Kinetic energy and Potential energy.

Heat (a part of the internal energy of a system E= q + w)

Heat, q, is also not a state function because it is the transfer of thermal energy. Therefore, it depends upon the pathway to the final position from the initial position. Heat and work are both lower case and are not state functions because you can only measure them during a change of a system. They depend on the what actually happens during a reaction for a system.