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Chapter 18 1st Law of Thermodynamics: U = Q(energy that flows through thermal contact) W(forced) State of a system: T, P, V.

. U depends only on state of system not how !t got there" (#lane tra!ns cars get you to $o%o&en") Q and W can ha'e many d!fferent 'alues and st!ll get you to the same U( W !s pos!t!'e !f the system does the wor& (energy goes down)" W !s negat!'e !f wor& !s done )* the system (energy goes up)" +emem%er that the !nternal energy can %e assoc!ated w!th the energy of the molecules ,!pp!ng around( -ealed can on a %urner"

. cyl!nder conta!ns /"0 moles of a monatom!c gas at an !n!t!al temperature of 12 3C" 4he gas !s compressed %y do!ng 560 7 of wor& on !t and !ts temperature !ncreases %y 180 C3" $ow much heat flows !nto or out of the gas9 We want: Q We &now: n 40 W 4f 4 ;uas!<stat!c happens so slowly that at any t!me the system !s !n e;u!l!%r!um w!th !ts en'!ronment" =!&e the chec&out l!ne at Wal<>art on Chr!stmas ?'e" # 4 are un!form throughout system" *o fr!ct!on or other d!ss!pat!'e forces"

re'ers!%le system and surround!ngs can %e returned to %eg!nn!ng state"

.ll @realA processes are !rre'ers!%le happen fast or fr!ct!on !s present" Constant pressure called ISOBARIC

.s gas eBpands C4 does wor& )* the p!ston (DW)"

+ecall E = #0." W = EFd = #0. (Bf B0) = #0 G" W = the purple area( Cf pressure !s *)4 constant !t -4C== wor&s(

Constant 'olume called ISOC ORIC what must %e ,ero9 W( Why9

$eat a sealed can on the sto'e" #ressure goes up 4 goes up %ut walls canHt mo'e so no wor& can %e done" U = Q

Csothermal #rocesses: -!nce #G=*&4 !f 4 !s constant then #G !s also constant( )r


#= constant G

Erom calculus W = *&4 ln

Gf G!

+ecall U = n+ (4f 4! ) for a monatom!c !deal gas" Cf 4 !s a constant what !s


U 9 Iero( -o Q = W"

8 1

-uppose 1/5 moles of a monatom!c !deal gas undergo an !sothermal eBpans!on 8 " m 8 to /"00 m as shown !n the f!gure" (a) What !s the temperature at the from 100 %eg!nn!ng and at the end of th!s process9 (%) $ow much wor& !s done %y the gas dur!ng th!s eBpans!on9

(a) T! = Tf =

Pf Vf (100 108 #a)(/"00 m8 ) = = 881 J 7 nR (1/5 mol) 8"81 mol J

(b)

.d!a%at!c #rocesses: Q = 0 means no heat flows !nto the system" 4h!s !s accompl!shed e!ther w!th good !nsulat!on or a 'olume change that happens so fast thereHs no t!me for heat to flow"

>ent!on that 4a%le 18<1< w!ll %e added to the formula sheet" S!ecific eats for an Idea" #as +ecall c !s amount of heat needed to ra!se the temperature of 1 &g of someth!ng %y 1 C3" Kut Q depends on type of process( We ha'e to spec!fy( >olar spec!f!c heats: (cap!tal @CA num%er of moles rather than mass)

C' = mol J
Q ' = nC ' 4

Constant 'olume process"

W=0

all heat used to

ra!se temp" Constant pressure process" WL 0 heat used to ra!se temp .*M do wor&" >ore heat !s re;u!red so Cp must %e =.+N?+" Eor a monatom!c !deal gas we can f!nd C' thusly: Q = U D W Q = U 8O1 + = C' Eor constant pressure: W = # G = n+4
8 5 Q p = U + W = n+4 + n+4 = n+4 1 1 5 Cp = + and C p C ' = + 1
Q p = nC p 4

Constant 'olume means that W = 0" U = 8O1 n+4 = Q ' = nC ' 4 compar!ng we see

. pretty good approB!mat!on for .== gases not Pust !deal monatom!c( .d!a%at!c processes:
#G = constant where = Cp C' = 5 %ut )*=Q for monatom!c gases( 8

R (a) Cf the !nternal energy of a system !ncreases as the result of an ad!a%at!c process !s wor& done on the system or %y the system9 (%) Calculate the wor& done on or %y the system !n part (a) !f !ts !nternal energy !ncreases %y 620 7" .d!a%at!c means that Q = 0"
(a)

U > 0 means that W > 0 so W is negative!

The work is done on the system.

(b)

SS C# .t constant pressure !t ta&es 110 7 of heat to ra!se the temperature of a g!'en !deal monatom!c gas %y 16 J" (a) Cs the amount of heat re;u!red to produce the same !ncrease !n temperature at constant 'olume greater than less than or the same as at constant pressure9 ?Bpla!n" (%) Meterm!ne the amount of heat re;u!red for the same temperature !ncrease at constant 'olume" Constant pressure: W = #G and Q = U D # G (a) *o wor& !s done %y the gas so all the heat added results !n an !ncrease !n !nternal energy" =ess heat !s re;u!red"
(b)

T =

Qp
5 nR 1

Q'
8 nR 1

8 8 Q' = Qp = (110 7) = 66 7 5 5
$nd Law of Thermodynamics: $eat flows from hot to cold (spontaneously)"-nowfla&e" .rrow of t!me" $eat eng!nes and the Carnot cycle: heat eng!ne con'erts heat to wor&"

1" Ko!l water (Q$)" 1" $ot steam w!ll flow toward cold reser'o!r (1nd =aw)" )n !ts way the steam eBpands the p!ston and does mechan!cal wor&" 8" -team g!'es off heat to atmosphere and re<condenses (Q=)" /" Water !s pumped %ac& up !nto the %o!ler" Wh!ch %r!ngs us to the +!chard Ma'!sson (wor&ed on the manhattan proPect) ;uote: T4here are no phys!c!sts !n the hottest parts of $ell %ecause the eB!stence of a Uhottest partU !mpl!es a temperature d!fference and any marg!nally competent phys!c!st would !mmed!ately use th!s to run a heat eng!ne and ma&e some other part of $ell comforta%ly cool" 4h!s !s o%'!ously !mposs!%le"T Q$ = Q= + W eff!c!ency: e = Q W Q$ QC = =1 C Q$ Q$ Q$

Carnot: Eor maB!mum eff!c!ency all processes must %e re'ers!%le" .ny 1 re'ers!%le eng!nes w!th same 4$ and 4C ha'e the same eff!c!ency" emaB = 1 4C 4$ 0 J9 What !f there !s no temp" d!fference9

Ct !s poss!%le to transfer heat from cold to hot !f you do W)+J" ?ntropy how messy !s !t9 - = Q 4

Tota" entro!y of %ni&erse increases when any irre&ersi'"e !rocess occ%rs. Re&ersi'"e !rocesses don(t chan)e the entro!y of the %ni&erse. $nd Law re*stated: entropy !s e'er<!ncreas!ng( M!scuss @heat death of the un!'erseA"

Mo l!'!ng systems '!olate th!s9 +rd Law: ,-. *o way"