8/9/2019 1-Thermo

1/7

COCOHALec

RE

TH

TH

RSE CORSE TITD-OUT Nure Hour

ERENCE

RMODYN

Is the

Is bas

many

Does

states

Basic

1.

2.

Mech

RMODYN

Syste

or ima

syste

Surro

Types

1.

2.

3.

Phas

syste

1.

2.

E :E :

O. 1 :s :

:

AMICS

study of in

ed on the

molecules

not consid

of a syste

forms of e

KINETI

POTEN

anical Eq

M

ElTh

AMIC SY

m is defin

ginary, for

undings i

of Syste

Open s

Closed

energy

Isolate

possible

is define

Homog

Heterog

CHPPHYFIRS1.50FundMaro

terrelation

behaviour

er the tim

m

nergy exis

ENERG

Possesse

body as a

IAL ENE

Possesse

body and

ivalent o

chanical

ctrical Enermal Ene

TEM

d as any

purposes

s the porti

:

stems ,

System ,

systems

as a ho

neous sy

eneous sy

Y2 34PICAL CH LAW OFours

amentalsand Lan

between

of macros

element i

ting in Na

d by a sys

whole

RGY

d by a sys

its configu

f Heat is t

nergy

rgyrgy

portion of

of study o

n of the u

Figu

hich can e

here no t

, where n

ogeneou

tem conta

stem cont

MISTRYTHERM

of Physico

various for

copic syst

in transfor

ure:

em by virt

em by virt

ration with

e relation

the univer

f the effec

niverse ex

e 1. Syste

xchange

ansfer of

exchang

, physicall

ins only o

ains more

2DYNAMI

al Chemi

ms of ene

ems or tho

ations b

ue of its

ue of its p

respect t

of the uni

cgs

JC

e isolated

t of variou

cluded fro

m and Su

oth matte

atter to o

of matter

y distinct,

e phase

than a sin

S

try

rgy in a sy

se of com

t intereste

otion, be i

sition, or

other bo

of mecha

Unitsrg

ulelorie

in an iner

s variable

m the syst

rounding

r and ener

r from the

and ener

and mech

gle phase

stem

paratively

d only in t

t molecula

by virtue o

ies

nical work

t containe

upon the

em

gy with its

surroundi

y with its

anically se

large and

he initial a

r or motio

f the struc

to the the

which m

contents

surroundi

ngs is pos

surroundi

parable p

involving

nd final

of the

ture of the

rmal units

y be real

f the

gs

sible, only

gs is

rtion of a

8/9/2019 1-Thermo

2/7

FIR

Phase

1.

2.

Types

1.

2.

Princi

by rep

T LAW

First l

neith

For a

appea

The in

E re

repre

Ther

chang

view :

That i

use:

E de

the ch

Work

is:

Since

s present

Pure su

Solution

of Proper

Extensi

Intensiv

ple of Re

roducing t

F THERM

w of Ther

r be crea

y quantity

r in total q

ternal ene

resents t

ents work

odynamic

e; and a s

, in this c

E = q + w

pends onl

ange is a

is defined

P = F/A, o

in a syste

bstance

An eleme

constituen

sTrue Solu

substance

May eithe

ties of a S

e Propert

Magnitud

Includes

e Property

Value is ithe subst

Includes d

roducibil

he values

ODYNAM

modynami

ted nor d

of a form

uantity ex

rgy of a s

e change

quantities

ign, indica

where the

the negati

nvention

in the ini

complishe

as a force

r F = P x

may co

t or comp

ts

ion is defi

s

r be gas, li

stem:

depends

ass, volu

dependennce or su

ensity, pr

lity of Sta

of the vari

ICS

ics is mer

stroyed

of energy

ctly equal

stem can

in the inte

always c

ting the di

positive

ive sign i

he signs

ial and fin

d

applied o

Wo

dw

, then

dw

nsist of:

ound whic

ned as a p

quid or sol

on the am

e and en

t of the totstances i

ssure, ref

tes sugge

ables

ly the law

that disap

l to the am

be chang

rnal energ

nsist of t

ection of t

ign indic

dicates th

f both q a

al states o

er a given

k = For

= F x

= p x

h contains

hysically

lid and ma

ount of su

ergy

al amount a syste

active ind

ts that th

of conser

ears, ano

ount that

d by a flo

y of the sy

o parts: a

he flow. T

tes that th

at the syst

nd w refle

f the syste

distance,

e x distan

h

x dh

a fixed a

omogene

y vary in c

bstance p

, but depe

ex, mass

State of

ation of e

ther or oth

isappear

of work,

stem, q re

number,

e sign re

e system

ems ener

t what ha

m, and no

if the pist

ce

d definite

us mixtur

ompositio

esent

nds on the

nd volum

system c

nergy, tha

er forms o

d.

heat or bo

presents

iving the

flects the

energy i

gy is decr

pens to t

t at all on

n moves

ratio amo

e of two o

within wi

concentr

e per mole

an be rep

is, energ

f energy

th:

eat, and

agnitude

systems

increasin

asing

e system;

he mann

distance

g its

more

de limits

tion of

oduced

can

ill have to

of the

point of

g

thus we

r in which

h, work

8/9/2019 1-Thermo

3/7

Since

And:

Differ

1.

2.

3.

4.

IMPO

1.

2.

3.

4.

5.

volume of

nt thermo

Consta

Opposi

Opposi

Opposi

V for th

can be

curve.

TANT!

The pre

but the

If V2 > V

surroun

If V2 < V

on the g

Magnitu

not a st

Since

process

the cylind

Fi

dynamic c

t Volum

ng Press

ng pressu

ng Press

work equ

erformed

ssure whi

ressure a

1, the pro

ing

1, the pro

as

de of wor

te functio

E is fixed,

er equals

dV

dw

ure 2. Pr

onditions:

, where d

E

re Zero o

E

re consta

dw

w

re Variab

ation to b

graphicall

h determi

gainst whi

ess is exp

ess is exp

depends

q must va

he area o

= final

= A x

= p x

= p d

ssure V

= 0, dw

= q

r Free Ex

= q

nt :

= p d

= p (V

le , when p

integrate

by plottin

es the a

ch the gas

ansion, w

ansion, w

on the ma

ry with w,

the pisto

volume

dh

x dh

olume or

0, hence

ansion ,

2 V 1)

is variabl

d. If no an

g p vs. V

ount of w

is workin

is negativ

is positive

nner in wh

nd thus d

times the

initial volu

echanica

:

here p =

, then p

lytic func

nd deter

rk done i

, and wor

, and wor

ich work i

ependent

height of

me

l Work

0, dw = 0

ust be kn

ion is avai

ining the

not the p

k is done

is done b

performe

upon the

the cylind

nd hence

own as a f

lable, the

area unde

ressure of

y the gas

y the surr

d, and, he

ath follow

r:

:

unction of

integration

r the

the gas

on its

unding

nce, w is

ed by the

8/9/2019 1-Thermo

4/7

RE

EN

ERSIBILI

Rever

infinit

oppos

Rever

irreve

The w

and th

The

Under

the pr

If the

work t

HALPY

Entha

where

of the

Since

functi

consi

volum

Since

Since

Henc

At co

is equ

the flo

heat

const

TY AND

sible Proc

simally gr

ing force

sible proc

sible in n

ork obtain

at this wo

maximu

reversibl

essure of t

riving pre

han PdV

F THE S

lpy or hea

E is the i

system

internal

n

er a proc

e work (w

H = E + P

P is const

:

stant pre

al to the e

w of heat

f reactio

nt pressu

AXIMUM

ess is any

eater than

y an infini

ss are im

ture

able from

k is the m

work is

condition

he gas its

M

ssure is m

ill be req

STEM

content o

ternal en

nergy, pr

ess carrie

= P V). U

V:

ant:

sure (whe

nergy flo

is a meas

and ch

re.

WORK

process

the oppo

tesimal a

possible i

a given pr

inimum re

btainabl

s, the exte

lf, P, hen

aximum

ade great

ired to ac

f the syste

rgy of the

essure, a

d out at c

nder thes

re only P

as heat.

re of the

nge in e

hich is co

ing force,

ount

nature, a

cess und

quired to r

from a s

rev

rnal press

ce:

ork (w m)

r the P +

omplish t

m is defin

system, P

d volume

onstant pr

condition

work is a

This mea

change in

nthalpy ar

ducted th

and which

d hence

r reversib

verse the

stem wh

rsible.

ure p diffe

= P dV

dP, the pr

e compre

d as:

is the pre

are all s

essure, w

s the expr

llowed) th

s that for

enthalpy f

e used i

at at ever

can be re

ll naturall

le conditio

process:

en any ch

rs only by

cess bec

ssion.

ssure of th

tate functi

here the

ession:

e change

a reactio

or the sys

terchang

stage the

versed by

occurrin

ns is the

ange taki

an infinite

me irreve

e system,

ions, enth

nly work

= q P + w,

in enthalp

studied

em. For t

ably for

driving fo

increasin

processe

aximum

ng place i

imal amo

rsible and

and V is t

alpy is al

allowed is

becomes

( H) of t

t constan

is reason,

eactions

rce is only

the

s are

ossible,

s entirely

unt from

more

he volume

o a state

pressure-

:

he syste

pressure,

, the term

studied a

,

8/9/2019 1-Thermo

5/7

TH

Hea

Hea

RMODYN

For a

where

tempe

its te

T is:

Molar

1 mol

ting a Ga

when

C v is t

When

be no

increa

ting a Ga

when

C P is t

When

Thus,transl

AMICS O

Ideal Ga

(KE) avg r

rature T (i

perature.

Heat Cap

of that s

at Cons

volume is

he rate of

an ideal

PV work

se the tra

at Cons

pressure i

he rate of

an ideal

when a gtional en

F IDEAL

: PV = nR

presents

n kelvins).

The ener

acity of a

bstance b

ant Volu

held const

change of

as is heat

V = 0).

slational

ant Pres

s held con

change of

gas is he

as is heatergy of

ASES

T, and:

he avera

The only

y (heat)

substanc

y 1 K.

C

dq

C

e:

ant, dV =

CV

the intern

ed in a rig

nder the

nergies o

ure:

stant, p =

CP

CP

the enthal

ted at co

ed at conhe gas

e, rando

way to ch

required

is define

= dq /

= dE

= dE

0:

=( E

l energy

id contain

e conditio

f the gas

P:

=( E

=( H

lpy with te

nstant pre

tant presand to p

, translati

nge the ki

o change

as the en

dT

p dV

p dV

T

/ T)V

ith tempe

er in whic

ns all the

olecules

/ T)P + P

/ T)P

perature

ssure, its

ure, ener ovide th

onal ener

netic ener

the energ

ergy requ

rature at c

no chan

energy th

( V / T)

at consta

volume in

gy must b work t

y for 1 m

gy of an i

y of 1 mol

ired to rais

onstant v

e in volu

t flows in

\

t pressur

creases a

e suppliede gas d

le of gas

eal gas is

e of an id

e the tem

lume

e occurs,

o the gas

nd PV wo

both to c

oes as i

at a given

to change

eal gas b

erature o

, there can

is used to

rk occurs.

hange the expand

.

8/9/2019 1-Thermo

6/7

Hea

The q

ting a Pol

Mona

gases

that a

As a

vibrati Temp

the g

transl

vibrati

Note

nonid

Rathe

proce

Thus,

Note

expec

availa

uantity of

yatomic

omic real

such as

e significa

olyatomic

onal motioerature of

s. Thus,

tional en

onal and r

hat the el

al behavi

r, it is sim

ses other

if a given

lso that a

ted becau

ble to abs

ork done

as:

gases, su

O 2 and

ntly great

gas is he

ns as wella monato

when a g

rgies of t

otational e

levated va

or. That i

ly that th

than tran

polyatomi

the mole

se the pr

rb energy

THE

as the ga

h as heliu

HCl3 that

r than 3/2

ated, the

as to moic ideal g

as is hea

he molec

nergies d

lue of Cv

s, it does

internal

lational m

gas obey

cules bec

sence of

RMMOD

expands

m, have

contain p

R.

as molec

e throughas is an i

ted, the t

les incre

es not co

for a gas

not depe

tructure o

otions.

s ideal ga

me more

more ato

NAMIC P

by V is

easured

olyatomic

ules absor

space (tradex of th

mperatur

se. Any

tribute dir

whose p

d on wh

f the mole

law, the

complex (

s means

OPERTI

V

alues of

molecule

b energy

nslate) ataverage

e only inc

nergy tha

ectly to th

articles ar

ther the

cules ena

quation b

more ato

that mor

S OF ID

v very clo

have ob

o increas

higher sprandom tr

reases to

t is abso

translati

e molecul

gas obey

les them

elow can

s), Cv inc

nontran

AL GAS

e to 3/2 R.

erved val

their rot

edsnslational

the exte

bed to in

nal kineti

es is not

the idea

to absorb

e used:

reases. Th

lational m

. However,

ues for C

tional and

l energy o

t that the

rease the

energy

caused b

l gas law.

energy fo

is result i

otions are

,

.

8/9/2019 1-Thermo

7/7

For calculation of the heat flow for an ideal gas:

q = nC T

where C V or C P is used depending on the conditions

For a temperature change of ideal gas regardless of whether pressure or volume (or neither) is

constant: H = n C P T

E = n C V T

Heat flow at constant volume equals E; ( E = q V)

Heat flow at constant pressure equals H; ( H = q P)

CARNOT CYCLE

Observations from Carnot Process:

1. Absorption of heat takes place at the higher temperature

2. Heat passes from higher to lower temperature

3. Thermodynamic efficiency must be the same for all processes operating under a given

temperature