Chapter 5 Thermochemistry: Energy Changes in Reactions

Energy (E) from chemical reactions produces the energy we use

E can be used to do work (electrical, mechanical, light, sound) and this cause motion ( location or
shape)
E can be transferred to another object and raise its T (state)
Measuring E is difficult, but measuring E is easier since measuring T is feasible
The fast majority of chemical reactions and all physical changes consume of release energy

Thermodynamics the study of energy and its transformations

Thermochemistry the study of the relation between chemical reactions and changes in heat energy
Thermochemical Equation the equation of a reaction that includes heat
Chemical energy is contained within the chemical bonds of a molecule
Energy (E) the ability to do work and/or transfer heat
Heat (q) energy transferred between objects due to a difference in temperature
o Energy transfer in the form of heat always flows from hot to cold
o Units must be E units: J (SI unit), kJ, cal, Cal (kcal)
Work (w) the energy required to move an object through a given distance (Force
distance)
Conservation of E can't be created or destroyed, must be converted
Thermal Equilibrium a condition in which T is constant throughout a material and no heat flows
State Function property based solely on its chemical or physical state or both, but not on how it
got there
o i.e. depends solely on the difference between initial and final states, path
INDEPENDENT
Potential Energy (PE) the energy stored in an object because of its position
o Can be converted to work PEg = mgh
o Chemical energy is a form of PE PEc heat
o It is a state function
Kinetic Energy (KE) KE= m u2
At the molecular level, T governs motion & chemical bonds and electrical charges give rise to PE
o Since T governs motion ( u ), T governs KE of atoms, ions, and molecules (Thermal Energy)
Thermal Energy (ThE) the KE associated w/ total random motion of molecules

ThE T
However, ThE depends on the number of molecules in a sample
A large sample of water has the same KE, but a larger ThE than a smaller
sample
o Electrostatic Potential Energy (Eel) the energy a particle has because of its position relative
to another particle, aka coulombic interaction

Eel

Q 1 Q2
d

(Coulombs Law)

if +Eel repulsive, -Eel attractive

Lower Eel = more stability (negative is more stable)
Ions are surrounded by a cloud of e-, so too close = repulsion
The potential energy at the atomic level (electrostatic attractions, not gravity)

total E, at atomic level, is KE (due to random motion) + PE (due to their arrangement)

E=ThE+Eel
System the part of the universe that is the focus of a thermochemical study
Surroundings everything that is not part of the system (Universe = system + surroundings)
(what you are
Isolated System system can not exchange energy or matter with surroundings
studying,
a Closed System system exchanges energy, but not matter with surroundings
often
SIGN matters
chemical
rxn,
Open System system exchanges both energy and matter with surroundings
chose such
that your life
is easier)

make sure it
is right!!!

Exothermic E flows from system to surroundings (INC in Tsurr) RELEASES HEAT qrxn < 0
Endothermic E flows from surroundings to system (DEC in Tsurr) ABSORDS HEAT qrxn > 0
Phase changes: gas liquid solid (exothermic); solid liquid gas (endothermic)
Combustion Reactions are always exothermic

Internal Energy sum of all KE and PE in a system (Translational, Rotational and Vibrational) a state
function
First Law of Thermodynamics - E gained/lost by a system must equal E lost/gained by the
surroundings
Esystem + Esurroundings = 0
Internal Energy E=q+w ; heat and work due to pressure and volume (P-V Work)
o
w=P V
associated with the expansion and compression of gas
work done by the system corresponds to Vsystem and transfers of E to surroundings
Enthalpy (H) the sum of the internal energy and the P-V Work of a system; H = E + PV just q
H= E+ P V
like E, H is difficult to measure, so use H (a state function)
Enthalpy Change (H) heat(energy) transferred for a reaction at constant pressure
o
&
H <0 exothermic
H >0 endothermic
o subscripts to specify: Hrxn, Hvap, Hsys, Hfus(melting), Hsolid(freezing/solidification), etc.
Enthalpy of Reaction/ Heat of reaction (Hrxn) the energy absorbed or given off by a chemical
reaction
Both E and H represent changes in state functions of a system:
E includes all the energy (heat and work) exchanged in a system with the surroundings ( E=q+ w ).
H is only q, the heat, exchanged at constant pressures ( H=q p ).
If a chemical reaction does not involve changes in volume, then E and H have very similar values.
If a reaction consumes or produces gas ( experiencing large changes in vol), E and H can be quite
different.
Chemical Reactions breaking (+/takes E) and forming (-/releases E) bonds
Average bond energies can be used to approximate the energy of the reaction ( Hrxn)
o Bond energy = the E needed to break 1 mole of covalent bonds in the gas phase (theres a
table)
o Hrxn = H(bonds breaking) - H(bonds forming)
Standard Condtions: 1bar/atm,
Standard Heat of Formations can be used also (the appendix in the book) some specified T, 25C
Standard State (SS) most
o Hrxn = Hf (products) - Hf (reactants)
stable form of a substance in
standard conditions
o Standard State Enthalpies (H) - H for rxns occurring in standard conditions
o Formation Reactions: 1 mole of a substance is formed from its component elements in their
Units of
Hrxn:
SS
Standard Enthalpy/Heat of Formation (Hf)
_______
use fractional coefficients if
___
Hcomb = Hf when the substance is a product and has only 1 mole in the equation
Hcomb is always negative because releasing heat
Formation reactions real life synthesis (proportions are equal, numbers (Es) are off)
qrxn = n Hrxn
Hf for any element is its standard state is zero

i.e. Hf (O2(g)) = 0 kJ/mol

Heating Curves and Heat Capacity

AB T of solid to MP q=n c P ,s T

q=n H fus

BC Constant T @ MP (process of melting)

CD T of liquid to BP

DE Constant T @ BP (process of boiling)

E+ T of gas to q=n c P ,g T
o Molar Heat of Fusion (Hfus) the energy required to convert 1 mole of a solid substance at
its melting point into the liquid state
o Molar Heat of Vaporization (Hvap) the energy required to convert 1 mole of a liquid
substance at its boiling point to the vapor state

q=n c P ,l T

q=n H vap

Must specify state and WATCH UNITS!!

Molar Heat Capacity ( c P ) the E required at constant pressure to raise the temp of 1 mole of a
substance by 1C
Units: J/molC
q=n c P T

Specific Heat ( c S ) the E required to raise the temp of 1g of a substance 1C at

constant pressure
Units: J/gC
q=g c S T

Water:

c P =75.3
(ice

J
mol C
J

37.1

c P =molar mass c S
mol C
Heat Capacity (CP) the quantity of E needed to raise the temp of an object 1C at constant pressure
Units: J/C

q=C P T
Water is special for many reasons, one is its high molar heat capacity:
it is able to absorb large quantities of energy it is used as a heat sink
heat sink matter that can absorb without changing phases or significantly changing its
temperature

Calorimetry the measurement of the quantity of heat transferred during a

physical change or chemical process

Calorimeter a device used to measure the absorption or release of

Calorimeter's Constant (Ccal) the heat capacity of a calorimeter
usually need to calculate this, which is called calibrating the
o qsys + qsurr = 0 (qrxn + qcal = 0); T = Tf Ti
o qcal = Ccal T; Ccal = qcal/T (J/C)
o Ccal = calorimeter constant (heat capacity)
o q is energy, when adding make suer they have the
Bomb Calorimeter: constant-volume calorimeter no PV work
Coffee Cup Calorimeter: constant pressure calorimeter
() qcal = -Ecomb (qcal = -Hcomb or -Hrxn)

E
calorimeter

same units!!

Hesss Law the standard enthalpy of reaction Hrxn for a reaction that is the sum of two or more
reactions is equal to the sum of the Hrxn values of the constituent reactions (enthalpy is a state function)
Example:

Standard Enthalpy of
Formation
(&Delta;Hf&deg;)
Standard Enthalpy of
Reaction
(&Delta;Hrxn&deg;)
Food Value
Fuel Density
Fuel Value

The enthalpy change of a formation reaction; also known as standard heat of formation or heat of formation.
The energy associated with a reaction that takes place under standard conditions; also known as standard heat of
reaction.
The quantity of energy produced when a material consumed by an organism for sustenance is burned completely;
it is typically reported in Calories (kilocalories) per gram of food.
The amount of energy released during the complete combustion of 1 liter of a liquid fuel.
The energy released during complete combustion of 1 g of a substance.