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热力学第二定律 PowerPoint PPT Presentation


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热力学第二定律. 热力学第二定律. 1. 热力学第二定律. 2. 卡诺循环和熵. 主要 内容. 3. 单纯 P 、 V 、 T 变化过程熵的计算. 相变过程熵的计算. 4. 5. 吉布斯函数及应用. 自发过程. · 气体向真空膨胀 · 高温物体传热给相接触的低温物体 · 浓溶液的扩散 · 锌片投入硫酸铜溶液中的反应 · 电解水的反应. 自发过程 : 无需外力帮助 , 任其自然 , 即可发生的过程。. 自发过程的共同特征. 自发过程的方向性归结为热功转换的方向性。.

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热力学第二定律

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1

2

3

PVT

4

5

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:,,

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1: Q=W=U=H=0, V>0

U=0, H=0, Q = W

2:

3: Cd(s)+PbCl2(aq)=CdCl2(aq)+Pb(s)

WQ QW ?

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!

,

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  • Clausius1850

,

  • Kelvin1851

,, ().

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1824 N.L.S.Carnot (1796~1832) W

N.L.S.Carnot

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T2

Q2

()=W/Q2

W

()= - Q1/W

Q1

T1

T1, T2

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1.

(p1V1T1)(p2V2T1)

2.

(p2V2T1)(p3V3T2)

3.

(p3V3T2)(p4V4T2)

4.

(p4V4T2)(p1V1T1)

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1

1molpV

AB

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2

BC

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3(TC)

DC

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4

DA

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ABCD

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2

4

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,W, ., 1

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1 2

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ABABBA

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entropyS

AB

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AB

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T>=

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Clausius

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>

=

>

=

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>

=

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3)

1

2

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QR

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255mol200kPa

  • (a)

  • (b)Pamb=lOOkPa

  • (c)

  • lOOkPaSSiso

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40dm32molA(s)

15molB(g)A(s)

Cp(As)=25Jmol-1K-1

25A(s)B(g)

75

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(H201)101325kPa100

H=40668kJmol-1

100101325kPa01m3(H20g)

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dU = Q + W = Q + We + W

=Q - pdV + W

TdSQ 0

TdSdUpdVW >0

>

<

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T1 = T2 =T

d(UpVTS) >W

G UpVTS HTS

T,pdGT,p < W GT, p < W

W=0, GT,p, W<0

0, =0,

0

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: GT(g)= nRT =nRT

G

GHTSUpVTS

GT = HTS

: GT = V (p2p1)

G=0

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Q w u h s g

QWU H S G

CV,m = 3/2R, Cp,m = 5/2R

CV,m = 5/2R, Cp,m = 7/2R

Qp=Qv+nRT

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