Chapter 5 Thermochemistry: Energy Changes in Reactions

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
Thermochemistry the study of the relation between chemical reactions and changes in heat energy
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 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 (state function)
o Can be converted to work PEg = mgh
o Chemical energy is a form of PE PEc heat
Kinetic Energy (KE) KE= m u2
At the molecular level
T governs motion ( u )
o T governs KE of atoms, ions, and molecules (Thermal Energy)
Thermal Energy (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 has the same KE, but a larger ThE, than a smaller sample
Chemical bonds and electrical charges give rise to PE
o Electrostatic Potential Energy (Eel) the E a particle has b/c of its position relative to another

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 (internal E) is KE (due to random motion) + PE (due to their

Universe = system (what you are studying) + surroundings (everything else)
Isolated System system can not exchange energy or matter with surroundings
Closed System system exchanges energy, but not matter with surroundings
Open System system exchanges both energy and matter with surroundings

SIGN matters

make sure it
Exothermic E flows from system to surroundings (INC in Tsurr) RELEASES isHEAT
qrxn < 0
right!!!

Endothermic + E flows from surroundings to system (DEC in Tsurr) ABSORDS HEAT qrxn >

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
1st Law of Thermodynamics - E gained/lost by a system = E lost/gained by surroundings
Esystem + Esurroundings
=0

E=q+w ; heat and work due to pressure and volume (P-V Work)
w=P V (associated with the expansion and compression of gas)

Internal E

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 (

H is only q, the heat, exchanged at constant pressures (

E=q+ w

).

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
Hrxn = Hf when the substance is a product and has only 1 mole in the equation
Hcomb is always negative because releasing heat
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

BC Constant T @ MP (process of melting)

CD T of liquid to BP

DE Constant T @ BP (process of boiling)

q=n c P ,l T
q=n c

q=n H fus
q=n H vap

E+ T of gas to
P ,g
Molar Heat of Fusion/Vaporization (Hfus/vap) the energy required to convert 1 mole of a solid/liquid substance at its mP/BP into the liquid/vapor state
Must specify state and WATCH UNITS!!
Molar Heat Capacity (
Intensive
properties
substance
by 1C
i.e. independent of

Units: J/molC

c P =molar mass c S

c P ) the E required at constant pressure to raise the temp of 1mol of a

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
q=g c S T
Units: J/gC

Heat Capacity (CP) the quantity of E needed to raise the temp of an object 1C at
constant pressure
q=C P T
Units: J/C

Water:

c P =75.3
(ice

37.1

J
mol C

J
mol C

This is proportional to the mass (mass, CP)

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 w/o changing phases or significantly
changing its temp
Calorimeter a device used to measure the absorption or release of E
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)
qrxn =
Bomb Calorimeter: constant-volume calorimeter
no PV work
n Hrxn, but
Coffee Cup Calorimeter: constant pressure calorimeter

calorimeter

Hesss Law Hrxn (the standard enthalpy of rxn) for a rxn that is the sum of two or more rxns is equal to the sum of the
Hrxn values of the constituent rxns
Food Value 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
Fuel Density the amount of energy released during the complete combustion of 1 liter of a liquid fuel
Fuel Value the energy released during complete combustion of 1 g of a substance
Always go back and check the sign of your answer
--- exo or endo?