The Nature of Energy

John W. Moore Conrad L. Stanitski Peter C. Jurs

http://academic.cengage.com/chemistry/moore

Energy (E) = the capacity to do work. Work (w) occurs when an object moves against a resisting force: w = (resisting force) x (distance traveled) w = F d

Chapter 6 Energy and Chemical Reactions

All energy is either Kinetic or Potential energy.

Stephen C. Foster Mississippi State University

The Nature of Energy

Kinetic energy (Ek) - Energy of motion
macroscale = mechanical energy random nanoscale = thermal energy periodic nanoscale = acoustic energy

Energy Units
joule (J) - SI unit (1 J = 1 kg m2s-2) 2.0 kg mass moving at 1.0 m/s (~2 mph): Ek = mv2 = (2.0 kg)(1.0 m/s)2 = 1.0 kg m2 s-2 = 1.0 J

Ek = mv2

(m = mass, v = velocity of object)

Potential energy (Ep) Energy of position. Stored E. It may arise from:

gravity: Ep = m g h (mass x gravity x height). charges held apart. bond energy.

1 J is a relatively small amount of energy. 1 kJ (1000 J) is more common in chemical problems.

Energy Units
calorie (cal) Originally: The energy needed to heat of 1g of water from 14.5 to 15.5 C. Now: 1 cal = 4.184 J (exactly)

Conservation of Energy
Energy can neither be created nor destroyed. It can only change form. Total E of the universe is constant. Also called the 1st Law of Thermodynamics.

Dietary Calorie (Cal) - the big C calorie Used on food products. 1 Cal = 1000 cal = 1 kcal

Conservation of Energy

Energy and Working

If an object moves against a force, work is done.
Lift a book
you do work against gravity. The books Ep increases.

Drop the book:

Ep converts into Ek The book does work pushing the air aside.

A diver: a) Has Ep due to macroscale position. b) Converts Ep to macroscale Ek. c) Converts Ek,macro to Ek,nano (motion of water, heat)

The book hits the floor

no work is done on the floor (it does not move). Ek converts to a sound wave and T of the book and floor

increase (Ek converts to heat).

Energy and Working

In a chemical process, work occurs whenever something expands or contracts. Expansion pushes back the surrounding air. On heating a balloon: The gas heats up The gas expands; the balloon swells. The gas does work pushing back the rubber and the air outside it.

Energy, Temperature, and Heating

Temperature is a measure of the thermal energy of a sample.

Thermal energy
E of motion of atoms, molecules, and ions. Atoms of all materials are always in motion. Higher T = faster motion.

Energy, Temperature, and Heating

Energy, Temperature, and Heating

Heat Thermal E transfer caused by a T difference. Heat flows from hotter to cooler objects until they reach thermal equilibrium (have equal T ).

Consider a thermometer. As T increases: Atoms move faster; on average get farther apart. V of the material increases. Length of liquid column increases.

Systems, Surroundings, and Internal Energy

System = the part of the universe under study
chemicals in a flask. my textbook.

Systems, Surroundings, and Internal Energy

Internal energy = E within the system because of nanoscale position or motion Einternal= sum of all nanoscale Ek and Ep
nanoscale Ek = thermal energy nanoscale Ep
ion/ion attraction or repulsion nucleus/electron attraction proton/proton repulsion ..

Surroundings = rest of the universe (or as much as needed)

the flask. perhaps the flask and this classroom. perhaps the flask and all of the building, etc.

Universe = System + Surroundings

Systems, Surroundings, and Internal Energy

Internal energy depends on Temperature
higher T = larger Ek for the nanoscale particles.

Calculating Thermodynamic Changes

Energy change = final E initial E E = Efinal Einitial A system can gain or lose E
SURROUNDINGS SYSTEM SURROUNDINGS SYSTEM

Type of material
nanoscale Ek depends upon the particle mass. nanoscale Ep depends upon the type(s) of particle.

Efinal
E > 0
E in

Einitial
E < 0
E out

Amount of material
number of particles. double sample size, double Einternal, etc.

Einitial

Efinal

E positive: internal energy increases

E negative: internal energy decreases

Calculating Thermodynamic Changes

No subscript? Refers to the system: E = Esystem E is transferred by heat or by work. Conservation of energy becomes: E = q + w
heat
SURROUNDINGS SYSTEM Heat transfer in q>0 Heat transfer out q<0

Heat Capacity
Heat capacity = E required to raise the T of an object by 1C. Varies from material to material. Specific heat capacity (c) E needed to heat 1 g of substance by 1C.

work

E = q + w
Work transfer in w>0 Work transfer out w<0

Molar heat capacity (cm) E needed to heat 1 mole of substance by 1C.

Note the same sign convention for q and w

Heat Capacity
For other amounts or for other T changes: Heat required = mass x specific heat x T q = m c T or Heat required = moles x molar heat capacity x T q = n cm T

Heat Capacity
Substance Elements C (graphite) Al(s) Fe(s) Cu(s) Au(s) Compounds NH3() H2O() H2O(s) CCl4() CCl2F2() Common solids wood concrete glass granite c (J g-1 C-1) cm (J mol-1 C-1) 0.720 0.902 0.451 0.385 0.129 4.70 4.184 2.06 0.861 0.598 1.76 0.88 0.84 0.79 8.65 24.3 25.1 24.4 25.4 80.1 75.3 37.1 132. 72.3

Heat Capacity
How much energy will be used to heat 500.0 g of iron from 22C to 55C? cFe = 0.451 J g-1 C-1. Heat required = q = m c T q = 500.0 g (0.451 J g-1 C-1)(5522)C q = 7442 J = +7.4 kJ

Heat Capacity
24.1 kJ of energy is lost by a 250. g Al block. If the block is initially at 125.0C what will be its final T? (cAl = 0.902 J g-1 C-1) q = m c T T = q / (m c) Cooling, q is negative: negative T = 24.1 x 103 J 250. g(0.902 J g-1 C-1)

T = Tfinal Tinital = 107 C + sign, E added to the system (the iron) Thus Tfinal = T + Tinital = 107 + 125C = 18C

Heat Capacity
A 215 g block of Cu at 505.0C is plunged into 1.000 kg of water (T = 23.4 C) in an insulated container. What will be the final equilibrium T of the water and the Cu? (cCu = 0.385 J g-1 C-1) q = m c T qCu = (215. g)(0.385 J g-1 C-1)(Tfinal 505.0) qH2O = (1000. g)(4.184 J g-1 C-1)(Tfinal 23.4) qCu + qH2O = 0 (conservation of E) qH2O = -qCu

Heat Capacity
215 g Cu (505.0C) + 1000. g H2O (23.4 C). Final T ?

qH2O = -qCu 4184(Tfinal 23.4) = -82.78(Tfinal 505.0) (4184 + 82.78)Tfinal = 41804 + 97906 Tfinal = 32.7C (Note: Tfinal must be between Thot and Tcold)

Conservation of Energy and Changes of State When heat is: Added to a system
q is positive the change is endothermic

Conservation of Energy and Changes of State A liquid cools from 45C to 30C, transferring 911 J to the surroundings. No work is done on or by the liquid. What is Eliquid? Eliquid = qliquid + wliquid qliquid = -911 J Eliquid = -911J here wliquid = 0 (qsurroundings = +911 J)

Removed from a system

q is negative the change is exothermic exothermic.

Water Boils:

H2O() H2O(g)

endothermic exothermic

Heat transfers from the liquid to the surroundings:

Steam Condenses: H2O(g) H2O()

Work occurs as the sample expands or contracts. Overall: E = q + w

Conservation of Energy and Changes of State A system does 50.2 J of work on its surroundings and there is a simultaneous 90.1 J heat transfer from the surroundings to the system. What is Esystem? Work done on the surroundings by the system Heat transfers from the surroundings to the system wsystem = -50.2 J qsystem = +90.1 J Esystem = qsystem + wsystem Esystem = -50.2 J +90.1 J = +39.9 J

Enthalpy: Heat Transfer at Constant P

Because E = q + w:
At Constant V:

E = qV

subscript V shows fixed V work requires motion against an opposing force. constant V = no motion, so w = 0.

At Constant P:

E = qP + watm= H + watm

Subscript P shows fixed P. watm = work done to push back the atmosphere H = enthalpy enthalpy. H = qp

Freezing and Melting (Fusion)

During freezing (or melting)
Substance loses (or gains) E, but T remains constant.
50

Vaporization and Condensation

Hfusion = qP = heat to melt a solid. Change solid liq liq gas liq solid Name enthalpy of fusion enthalpy of vaporization enthalpy of freezing enthalpy of condensation etc. value for H2O (J/g) 333 2260 333 2260

Temperature (C) -25 0 25

Example: Convert 1 g of ice at -50C to water at +50C

Ice is melting. T remains at 0C

gas liq
Water warms from 0 to 50C

Note: Hfusion = Hfreezing

Ice warms from -50 to 0C 0 100 200 300 400 500 Quantity of energy transferred (J) 600

qfusion = qfreezing

-50

State Functions and Path Independence

State functions Always have the same value whenever the system is in the same state. Two equal mass samples of water produced by: State functions 2. Cooling the other from 100C to 50C. H E have identical final H (and V, P, E). P V T etc. State function changes are path independent. independent H = Hfinal Hinitial is constant. 1. Heating one from 20C to 50C.

Thermochemical Expressions
H = qP can be added to a balanced equation.
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g) H = 803.05 kJ CH4(g) + 2 O2(g) CO2(g) + 2 H2O() H = 890.36 kJ

H is the standard enthalpy change

P = 1 bar. T must be stated (if it isnt, assume 25C). H is a molar value. Burn 1 mol of CH4 with 2 mol O2 to

form 2 mol of liquid water and release 890 kJ of heat

Change a physical state, change H : H2O() vs. H2O(g)

Thermochemical Expressions
The thermite reaction produces tremendous heat: 2 Al + Fe2O3 Al2O3 + 2 Fe H = 851.5 kJ How much heat is released when 10.0 g of Al reacts with excess Fe2O3 at constant P ? nAl = 10.0 g / 26.982 g/mol = 0.3706 mol Al 2 Al 1 H = 851.5. kJ 851.5 kJ qp = 0.3706 mol Al = 158 kJ 2 mol Al

Where Does the Energy Come From?

Bond Enthalpy (bond energy) Equals the strength of 1 mole of bonds
Always positive
It takes E to break a bond Separated parts are less stable than the molecule. Less stable = higher E

E is always released when a bond forms

Product is more stable than the separated parts. More stable = lower E

Bond Enthalpies
During a chemical reaction: Old bonds break: requires E (endothermic) New bonds form: releases E (exothermic) Both typically occur: H2(g) + Cl2(g) 2 H(g) + 2 Cl(g) 2 HCl(g)

Bond Enthalpies
Overall, heat may be absorbed or released: Exothermic reactions (H < 0)
New bonds are more stable than the old,
energy less stability

E is released.

reactants products

or More bonds are formed than broken.

Endothermic reactions (H > 0)

E is absorbed.
exothermic H= -862 kJ/mol

endothermic H= +678 kJ/mol

New bonds are less stable than the old,

energy less stability

products reactants

or Fewer bonds are formed than broken

Measuring Enthalpy Changes

Heat transfers are measured with a calorimeter. calorimeter Common types:
Bomb calorimeter.
rigid steel container. filled with O2(g) and a small sample to be burnt. constant V, so qV = E

Measuring Enthalpy Changes

Bomb Calorimeter Measure T of the water. Constant V: Conservation of E: qreaction + qbomb + qwater = 0 or qreaction = qbomb + qwater with qbomb = mcalccalT = CcalT
A constant for a calorimeter

qV = E

Flame calorimeter.
samples burnt in an open flame. constant P, so qp = H

Coffee-cup calorimeter in lab (constant P).

Measuring Enthalpy Changes

Octane (0.600 g) was burned in a bomb calorimeter containing 751 g of water. T increased from 22.15C to 29.12C. Calculate the heat evolved per mole of octane burned. Ccal = 895 JC-1. 2 C8H18() + 25 O2(g) 16 CO2(g) + 18 H2O()

Bomb Calorimetry
T = 22.15 29.12C. Heat per mol octane (0.600 g) burned. 2 C8H18() + 25 O2(g) 16 CO2(g) + 18 H2O()

qreaction = qbomb + qwater qreaction = +6238 J + 2.190 x 104 J = 2.81 x 104 J = 28.1 kJ qreaction = 28.1 kJ

qreaction + qbomb + qwater = 0 qbomb = CcalT = 895 JC-1 (29.12 22.15)C = +6238 J qwater = m c T = 751 g (4.184 J g-1 C-1)(29.12 22.15)C = +2.190 x 104 J

Measuring Enthalpy Changes

Octane (0.600 g) Calculate the heat evolved per mole of octane burned

Measuring Enthalpy Changes

CoffeeCoffee-cup calorimeter Nested styrofoam cups prevent heat transfer with the surroundings. Constant P. T measured. q = qp = H Assume the cups do not absorb heat. (Ccal = 0 and qcal = 0)

Molar mass of C8H18 = 114.23 g/mol. nC8H18 = (0.600 g) / (114.23 g/mol) = 0.00525 mol C8H18 Heat evolved /mol octane = 28.1 kJ 0.00525 mol

= 5.35 x 103 kJ/mol = 5.35 MJ/mol

Measuring Enthalpy Changes

1.02 g of Mg was reacted with excess 1 M HCl(aq) (255.0 g) in a coffee-cup calorimeter. Tsoln rose from 22.0 to 41.6C. cHCl = 3.90 J g-1C-1 . Complete: Mg(s) + 2 HCl(aq) H2(g) + MgCl2(aq) H = ? qsoln = msoln c T (msoln = macid + mMg ) = 256.0 g (3.90 J g-1 C-1)(41.6 22.0)C = 1.957 x 104 J

Measuring Enthalpy Changes

1.02 g Mg + 255.0 g of acid. T: 22.0 42.5C. Molar H = ?

qrxn = 19.57 kJ = H for 1.00 g 1 mol = 0.04196 mol 24.31 g H = 466 kJ exothermic

nMg = 1.02 g

So Conservation of E: qrxn = qsoln qsoln + qrxn = 0 qrxn = 19.57 kJ = H

H = 19.57 kJ 0.04196mol 1 mol Mg

or

Hesss Law
If the equation for a reaction is the sum of the equations for two or more other reactions, then H for the 1st reaction must be the sum of the H values of the other reactions.

Hesss Law
Multiply a reaction, multiply H. Reverse a reaction, change the sign of H. 2 CO(g) + O2(g) 2 CO2 (g) Then 2 CO2(g) 2 CO(g) + O2(g) H = 566.0 kJ H = 1(566.0 kJ) = + 566.0 kJ H = 2(566.0 kJ) = +1132.0 kJ

Another version:
H for a reaction is the same whether it takes place in a single step or several steps.

H is a state function

4 CO2(g) 4 CO(g) + 2 O2(g)

Hesss Law
Use Hesss Law to find H for unmeasured reactions. Example It is difficult to measure H for: 2 C(graphite) + O2(g) 2 CO(g) Some CO2 always forms. Calculate H given: C(graphite) + O2(g) 2 CO(g) + O2(g)
No phase confusion

Hesss Law
Want: Have: A B 2 C + O2 C + O2 2CO + O2 2 CO CO2 2 CO2 ??? 393.5 kJ 566.0 kJ

+2 x A 1 x B

2C + 2O2 2CO2 2CO2 2CO + O2

2(393.5) = 787.0 1(566.0) = +566.0 221.0

CO2(g) 2 CO2(g)
drop phases

H = 393.5 kJ H = 566.0 kJ

2C + 2O2 + 2CO2 2CO2 + 2CO + O2 2 C + O2 2 CO

H = 221.0 kJ

Hesss Law
Determine H for the production of coal gas:
2 C(s) + 2 H2O(g) Using: C(s) + H2O(g) CO(g) + H2O(g) CH4(g) + H2O(g) CO(g) + H2(g) CO2(g) + H2(g) H = 131.3 kJ H = 41.2 kJ A B C CH4(g) + CO2(g)

Hesss Law
Want: Have: A B C 2 C + 2 H2O C + H2O CO + H2O CH4 + H2O CH4 + CO2 CO + H2 CO2 + H2 CO + 3 H2 ??? 131.3 kJ 41.2 kJ 206.1 kJ

+2 x A 1 x C +1 x B

2 C + 2 H2O 2 CO + 2 H2 CO + 3 H2 CH4 + H2O CO + H2O CO2 + H2 2C + 2H2O CH4 + CO2

+262.6 206.1 41.2 15.3 kJ

CO(g) + 3 H2(g) H = 206.1 kJ

No phase confusion

drop phases

(After cancelling and adding)

Standard Molar Enthalpy of Formation

Hesss law problems often use a combustion or Formation reaction Make 1 mol of compound from its elements in their standard states. H2 combustion:
2 H2(g) + O2(g) 2 H2O() 1 H2O() H = 571.66 kJ Hf = 285.83 kJ
f = formation

Standard Molar Enthalpy of Formation

Standard state = most stable form of the pure element at P = 1 bar. e.g. C standard state = graphite (not diamond) Hf for any element in its standard state is zero.
(take 1 mol of the element and make 1 mol of element)

but the formation reaction is:

H2(g) + O2(g)

Hf (Br2() ) = 0 Hf (Br2(g) ) 0

at 298 K at 298 K

Standard Molar Enthalpy of Formation

Appendix J (25C)
Compound Al2O3(s) CaO(s) Hf, kJ/mol 1675.7 635.09 74.81 +226.73 +52.26 84.68 277.69 241.818 285.830 573.647 aluminum oxide calcium oxide methane acetylene ethylene ethane

Standard Molar Enthalpy of Formation

H ={(nproducts)(Hf products)} {(nreactants)(Hf reactants)}

Notes Most are negative (formation releases E), but can be positive.
If the physical state

CH4(g) C2H2(g) C2H4(g) C2H6(g)

Example Calculate H for: CH4(g) + NH3(g) HCN(g) + 3 H2(g) H = Hf(HCN) + 3Hf(H2) Hf(NH3) Hf(CH4) = +134 + 3(0) (46.11) (74.85) = 255 kJ

changes, Hf changes.

C2H5OH(l) ethanol H2O(g) H2O(l) NaF(s) water vapor liquid water sodium fluoride