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一 晶格能的定义 PowerPoint PPT Presentation


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晶格能及其应用. 晶格能 又称点阵能。被定义为在 0K 、 1 个标准压力下 , 1mol 离子晶体转化成相互无限远离的气态离子时内能的变化值,用符号 L 0 表示。 (1mol) MX n M n+ (g) + nX - (g) L 0 =△ U 0 θ 一般地,为了方便,设 L T = L 0 设此过程中的焓变为△ H T θ △H T θ =△ U T θ +△ n(g)RT 根据前面所述,对于实验化学家来说,焓和能的概念是严格区分的,但数据上是混淆使用的,因此可将上式中的△ n(g)RT 忽略。于是

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一 晶格能的定义

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4848069

0K1, 1molL0

(1mol) MXn Mn+(g)nX(g)

L0U0LTL0

HT HTUTn(g)RT

n(g)RT

HTUtLTL0

1molSI


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MgOCaOAl2O3

NaCl6CsCl8ZnS4


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L (1 )

NAMZ+Ze2 1

40r0 n

NA

M

(Madelung)

(

21)Z+Ze0r0

n(2.2)


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, n NaClNa+Ne7ClAr9NaCln(79)/28

1.389105MZ+Z 1

r0 n

L0 (1 ) kJmol1

M: M(n++n,n+n), M/0.8( ) 34.5


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L0 1.214105 (134.5/r0)

ZZ

r0

ZZ

r0

L0 1.079105

1.389105MZ+Z 1

r0 n

L0 (1 ) kJmol1


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L0 1.389105M (11/n)

1.3891051.74811(11/8)/276

770 kJmol1

ZZ

r0

ZZ

r0

ZZ

r0

L0 1.214105 (134.5/r0)

1.214105211(134.5/276)/276

770kJmol1

L01.079105

1.079105211/276

782 kJmol1

NaCl


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NaCl(s) Na(g) + Cl(g)

L I Ea

Na(g) + Cl(g)

fHmS 1/2 B

Na(s) + 1/2 Cl2(g)

NaCl

L (SI)Na(1/2 BEa)ClfHm

(Born-Haber Cycle)

L 108.7496121.7368.5411769 kJmol-1


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CrCl(s) Cr(g) + Cl(g)

L I Ea

Cr(g) + Cl(g)

fHm S 1/2 B

Cr(s) + 1/2 Cl2(g)

1

, Cr3d54s1Cr14s3d5CrX(XFClBrI)CrClCrCl(NaCl)

L (SI)Cr(1/2 BEa)ClfHm

Cr+100 pm, rCl-181 pm,

L 1.214105211(134.5/281)/281758 kJmol-1

fHm (CrCl) 397653121.7368.575845 kJmol-1


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CrCl2CrCl(fGm 45 kJmol1), CrCl

2 CrCl(s) CrCl2(s)Cr(s)

fHm/ kJmol-1 45 396 0

fGm rHm (396) 245

486 kJmol1

CrClCrCl


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2

CrCl

1

, ,1962 N.Bartlett() Xe[PtF6],

PtF6O2

PtF6 ,PtCl6O2O2[PtF6]

O2 PtF6 O2[PtF6]


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O2[PtF6], Xe,

Xe[PtF6]

  • XeO2:

    • I1/kJmol1 Xe: 1170 O2: 1175.7

XeO2400 pm, Xe+O2+(O2+180 pm)

O2[PtF6]Xe[PtF6](PtF6310 pm)

L(Xe[PtF6])1.214105211(134.5/490)/490

461 kJmol1


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rHm

Xe(g) PtF6(g) Xe[PtF6]

I1 Ea L

Xe(g) PtF6(g)

  • rHm (Xe[PtF6])I1 Ea L

    • 1170(771)465

    • 60 kJmol1

XePtF6Xe[PtF6]60 kJmol1, ,PtF6XeCCl4Xe[PtF6]Xe[PtF6]


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2 O2

1O2PtF6O2PtF6

O2 O2e IHm(O2)1175.7 kJmol1

IHm(O)1314 kJmol1

O2O2F2FBF3BF4O2

O2 (g) 1/2F2 (g) BF3 (g)O2BF4 (s)

H

O2 (g) 1/2F2 (g) BF3 (g) O2BF4 (s)

O2+(g) F(g) BF3 (g) O2(g)BF4 (g)

HIHm(O2)IHm(F)H1latHm

H

fHm(F)

fHm(O2)

latHm(O2BF4)

H1


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H1 BF3 (g)F(g) BF4 (g)

fHmkJmol11137 270.7 1785.2

H1377.5 kJmol1

O2BF4latHm(O2BF4)

r(BF4)228pmr(O2)O22180 pmO2O22r(O2)<r(O22)r(O2)r(O22)180 pm

latHmL(O2BF4) (1 )

545 kJmol1

HIHm(O2)IHm(F,g)H1latHm

1175.7270.7377.554517.5 kJmol1

GHTSS<58.7JK1mol1G>0G

1.214105211 34.5

228180 408


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r(O2)r(O22)L(O2BF4)545 kJmol1H<17.5 kJmol1G0O2BF4GHTSS<0G

1964

O2BF4 O21/2F2BF3


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3

AM3

:


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26

69

89

112

24

,, ,-

,

50 kJmol1


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