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Thermochemistry
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!!! .
Energy is the capacity to do work
• Radiant energy comes from the sun and is
earth’s primary energy source
!!! .
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• Thermal energy is the energy associated with
the random motion of atoms and molecules
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• Chemical energy is the energy stored within the
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bonds of chemical substances
• a
Nuclear energy is the energy stored within the
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collection of neutrons and protons in the atom
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6.1
Energy Changes in Chemical Reactions
Heat is the transfer of thermal energy between two bodies that
are at different temperatures.
!!! .
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Temperature is a measure of the thermal energy.
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Temperature = Thermal Energy
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900C
400C
greater thermal energy
6.2
Thermochemistry is the study of heat change in chemical
reactions.
The system is the specific part of the universe that is of
!!! .
interest in the study.
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!!! .
2H2 (g) + O2 (g) 2H2O (l) + energy
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H2O (g) H2O (l) + energy
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a
Endothermic process is any process in which heat has to be
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supplied to the system from the surroundings.
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6.2
Exothermic
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Endothermic !!! .
6.2
Thermodynamics is the scientific study of the
interconversion of heat and other kinds of energy.
!!! .
of the system, regardless of how that condition was achieved.
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energy, pressure, volume, temperature
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∆E = Efinal - Einitial
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a ∆P = Pfinal - Pinitial
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∆V = Vfinal - Vinitial
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∆T = Tfinal - Tinitial
!!! .
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∆Esystem + ∆Esurroundings = 0
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or
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∆Esystem = -∆Esurroundings
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C3H8 + 5O2 3CO2 + 4H2O
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!!! .
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q is the heat exchange between the system and the surroundings
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w is the work done on (or by) the system
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w = -P∆V when a gas expands against a constant external pressure
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6.3
Work Done On the System
w=Fxd
w = -P ∆V
!!! .
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∆V > 0
F
PxV= x d 3
=Fxd=w -P∆V < 0
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d2
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wsys < 0
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Work is
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not a
state
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function!
∆w = wfinal - winitial
!!! .
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against a constant pressure of 3.7 atm?
w = -P ∆V
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(a) ∆V = 5.4 L – 1.6 L = 3.8 L P = 0 atm
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W = -0 atm x 3.8 L = 0 L•atm = 0 joules
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!!! .
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∆E = q + w
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q=0
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w < 0, ∆E < 0
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∆E = C∆T
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∆T < 0, SNOW!
Enthalpy and the First Law of Thermodynamics
∆E = q + w
At constant pressure:
!!! .
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q = ∆H and w = -P∆V
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∆E = ∆H - P∆V
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∆H = ∆E + P∆V
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6.4
Enthalpy (H) is used to quantify the heat flow into or out of a
system in a process that occurs at constant pressure.
∆H = H (products) – H (reactants)
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∆H = heat given off or absorbed during a reaction at constant pressure
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Is ∆H negative or positive?
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System absorbs heat
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Endothermic
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a ∆H > 0
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Is ∆H negative or positive?
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System gives off heat
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Exothermic
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a ∆H < 0
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!!! .
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H2O (s) H2O (l) ∆H = 6.01 kJ
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• If you reverse a reaction, the sign of ∆H changes
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H2O (l) H2O (s) ∆H = -6.01 kJ
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• If you multiply both sides of the equation by a factor n,
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then ∆H must change by the same factor n.
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6.4
Thermochemical Equations
!!! .
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H2O (s) H2O (l) ∆H = 6.01 kJ
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H2O (l) H2O (g) ∆H = 44.0 kJ
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How much heat is evolved when 266 g of white
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phosphorus (P4) burn in air?
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P4 (s) + 5O2 (g) P4O10 (s) ∆H = -3013 kJ
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1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4
6.4
A Comparison of ∆H and ∆E
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P∆V = 1 atm x 24.5 L = 2.5 kJ
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∆E = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol
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6.4
The specific heat (s) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
substance by one degree Celsius.
!!! .
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The heat capacity (C) of a substance is the amount of heat
(q) required to raise the temperature of a given quantity (m)
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of the substance by one degree Celsius.
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C=mxs
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Heat (q) absorbed or released:
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q = m x s x ∆t
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q = C x ∆t
∆t = tfinal - tinitial
6.5
How much heat is given off when an 869 g iron bar cools
from 940C to 50C?
!!! .
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s of Fe = 0.444 J/g • 0C
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∆t = tfinal – tinitial = 50C – 940C = -890C
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q = ms∆t = 869 g x 0.444 J/g • 0C x –890C = -34,000 J
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6.5
Constant-Volume Calorimetry
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qsys = qwater + qbomb + qrxn
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qsys = 0
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qrxn = - (qwater + qbomb)
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qwater = m x s x ∆t
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qbomb = Cbomb x ∆t
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Reaction at Constant V
∆H = qrxn
∆H ~ qrxn
No heat enters or leaves!
6.5
Constant-Pressure Calorimetry
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qsys = qwater + qcal + qrxn
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qsys = 0
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qrxn = - (qwater + qcal)
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qwater = m x s x ∆t
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qcal = Ccal x ∆t
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Reaction at Constant P
∆H = qrxn
!!! .
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1 cal = 4.184 J
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1 Cal = 1000 cal = 4184 J
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Substance ∆Hcombustion (kJ/g)
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Apple -2
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Beef -8
Beer -1.5
Gasoline -34
Because there is no way to measure the absolute value of
the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?
!!! .
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Establish an arbitrary scale with the standard enthalpy of
formation (∆H0f ) as a reference point for all enthalpy
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expressions.
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Standard enthalpy of formation (∆H0f) is the heat change
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that results when one mole of a compound is formed from
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its elements at a pressure of 1 atm.
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aA + bB cC + dD
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∆Hrxn
0
= [ c∆H0f (C) + d∆H0f (D) ] - [ a∆H0f (A) + b∆H0f (B) ]
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∆Hrxn
0
= Σ n∆H0f (products) - Σ m∆Hf0 (reactants)
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Hess’s Law: When reactants are converted to products,
the change in enthalpy is the same whether the reaction
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CO (g) + 1/2O2 (g) CO2 (g)
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6.6
Calculate the standard enthalpy of formation of CS2 (l)
given that:
C(graphite) + O2 (g) CO2 (g) ∆Hrxn 0
= -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) ∆Hrxn
0
= -296.1 kJ
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CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) ∆H0rxn = -1072 kJ
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1. Write the enthalpy of formation reaction for CS2
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C(graphite) + 2S(rhombic) CS2 (l)
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2. Add the given rxns so that the result is the desired rxn.
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C(graphite) + O2 (g) CO2 (g) ∆Hrxn
0
= -393.5 kJ
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!!! .
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2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)
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∆Hrxn
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= Σ n∆H0f (products) - Σ m∆Hf0 (reactants)
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∆Hrxn
0
= [ 12∆H0f (CO2) + 6∆H0f (H2O)] - [ 2∆Hf0 (C6H6) ]
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∆Hrxn
0
= [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ
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-5946 kJ
= - 2973 kJ/mol C6H6
2 mol
6.6
Chemistry in Action: Bombardier Beetle Defense
!!! .
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C6H4(OH)2 (aq) C6H4O2 (aq) + H2 (g) ∆H0 = 177 kJ/mol
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H2O2 (aq) H2O (l) + ½O2 (g) ∆H0 = -94.6 kJ/mol
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H2 (g) + ½ O2 (g) H2O (l) ∆H0 = -286 kJ/mol
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!!! .
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Which substance(s) could be
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used for melting ice?
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Which substance(s) could be
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6.7
The Solution Process for NaCl
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