Chem.412 – PChem I - OutlineChem.412 – PChem I - Outline

Introduction/Basics Review

Computer Applications States of Matter Equations of State

First Law of TD Molecular Energies Entropy – 2nd/3rd Laws

Equilibrium & Spontaneity

Quantum Chemistry

Introduction: Review of Basics

Four Major Principles

Mathematical Basics

Units Significant Figures. Factor Labels

Problem Solving

Common Terminology

States of MatterStates of Matter

Equations of State

Ideal Gas Deviations Mixtures

Van der Waals Virial Series Berth., R-K

Kinetic Molecular Model

Corresponding States

Fluids

Reduced Variables

Condensed Phases

nRTPV

nn PbPbPbRT

M

P ...1 2

21

nRTnbVV

anP

2

2

nb

Vn

aP

nRTV

i

i

21

...1432

V

nE

V

nD

V

nC

V

nBZ

Chem.412 – Molecular Energies

T ranslational

SpectroscopyHeat CapacityT heory vs. Experim ent

Experim ental M easures

Equipartition of Energy

Rotational V ibrational

Conservation of Energy

Equipartition of EnergyEquipartition of Energy

Motions

Linear Molecule Energy

per DOF

Non-Linear Molecule

DOF Energy DOF Energy

Translational 3 (3/2)kT (1/2)kT 3 (3/2)kT

Rotational 2 kT (1/2)kT 3 (3/2)kT

Vibrational 3N-5 (3N-5)kT kT 3N-6 (3N-6)kT

Heat Flow

Oth Law

Internal EnergyEnthalpy

Heat & W ork

Energy

1st Law

Reaction Spontaneity

Energy Distribution

Entropy

2nd Law

Zero K

3rd Law

Law s of Therm odynam icswqdU dVPw

Hq

Uq

P V

VV

PP T

UC

T

HC

&

R nCC VPR nCC VP

PVUH

)( grxnrxn nRTUH

Tem perature

Phase T ransitions

Heat Engines

Zero Entropy for Perfect CrystalsDow n to Zero K3rd Law Entropies

3rd Law of Therm odynam ics

Entropy of the Universe

Carnot Cycles Heat Pum ps

Supercooled Calculations Reversible vs. Irreversible

Volum e Pressure

Entropy Changes

2nd Law of Therm odynam icsEntropy/Disorder

Disbursem ent of Energy

Entropy - 2nd & 3rd Law s of Therm odynam ics

T

qdS rev

dPVdSTdH

dVPdSTdU

:(2) ME

:(1) ME V

dVnR

T

dTC

P

dPnR

T

dTCS VP

pt

ptpt T

HS

0 surr

osys

ounivo SSS

Helm holtz Free Energy (A)

Clapeyron

Standard StatesGibbs-Helm holtzTem perature Dependence

Phase Equilibrium Clausius-Clapeyron

M aster Equations

Spontaneity Indicator G ibbs Free Energy (G)

Free Energy Functions

A = U - TS G = H - TS

If Asys< 0, rxn spontaneous.

(Constant V & T)

If Gsys< 0, rxn spontaneous.

(Constant P & T)

dA = -PdV – SdT dG = VdP - SdT

pt

pt

VT

H

dT

dP

)ln( Prxn

o KRTG

dPVdSTdH

dVPdSTdU

:(2) ME

:(1) ME

dTSdPVdG

dTSdVPdA

:(4) ME

:(3) ME

STHG

Chem.412 – PChem I - OutlineChem.412 – PChem I - Outline

Introduction/Basics Review

Computer Applications States of Matter Equations of State

First Law of TD Molecular Energies Entropy – 2nd/3rd Laws

Equilibrium & Spontaneity

Quantum Chemistry