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发表于 2019-9-13 23:46:11 | 显示全部楼层 |阅读模式
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1????????????????????? 2?????????

3?????????????? 4???????????? ??????

????????????????????????????????

4.1

???????????????

4.2

??

??????????? ?????????

????????????

??? ???????????????

?

????????????????????????????????

4.3

?? ?????????????????

??????

??????

?????????????????????4.3????????

4.4

??4.4???????

?

?????????????

?

??????

4.5

??4.5???????????t???x??c0??????????????????k2??????????????????????????????????CH3COONa

+--?????????????Na??????OH??????CH3COO?????????

--??????OH?????CH3COO????????????????????????G????????k2?

??????????????x???????

4.6

4.7

??

?

???????

??? ???????

?????????4.6???4.7??????4.5????

????

4.8

?????

??? ??????

??

?

???????????????????? ???

????????

????????????????

?

?????4.4???????????? ????????

1???

????(?DJS-1?????)1?????1??????1????1?????(10ml)3???????(200ml)1?? 2???

NaOH???(0.0200moldm-3)?????(A.R.)????? ??????

1. ????

-1

???NaOH????(?0.0200 mol L)??????????????:?????

-1

???????????????250mL0.0200 mol L (?NaOH??????)???????????????????V????l mL?????V ml??????250 ml??

-1

???????????0.0200 mol L?????????

2. ?????

?????????(25.00.1)???(30.00.1)??? 3. ??????

4. ????????0???

-1

????200 ml?????????????50 ml 0.0200 mol L?NaOH ???????????????????????????????????????????? (???????2 cm)????15 min????????????????????????????????????????0?

5. ???????t???

-1

??????50 ml 0.0200 mol L?CH3COOC2H5??????200 mL???????

-1

????????50 ml 0.0200 mol L?NaOH????????200 ml?????????????????????15 min????????????????????????????????????????NaOH????????CH3COOC2H5??????????????????????????????????????????????????????????(??????)?????????kt??4 min?6 min?8 min?10 min?12 min?15 min?20 min?25 min?30 min?35 min?40 min??????????kt??????t?

6. ??????0?kt???

????????(35.00.1)???(40.00.1)???????4?5????????????o?kt??????t???????4 min?6 min?8 min?10 min?12 min?15 min?18 min?21 min?24 min?27 min?30 min???????????????????????????????????????? ??????????

1????

G0?Gt

?t,????????k?

Gt?G?

kT2kT1

?EaR

?T2?T1??? ?Ea?

?TT12?

2?????????k??ln

1????????????????????????????????????2?3?????????????????????????????????????

2?????????????????

3??????????????????????????????CO2??????2-?CO3?

4???????????????????? ?????

1????????????????????????????????????????

2???????????????????????????????????????

3?????????????????????????????????????????

4???????????????????????????k??????

??????????????????

?????????

????=25.00? ?0=1880?scmV????=10.00mL[????]=0.0200 mol/L VNaOH=10.00mL[NaOH]= 0.0200 mol/L

??????t?

?0??t

t

??,????m???m?

1

?????? kc0

?????m1=18.98

k1 =1/(mc0)=1/(18.980.0100) =5.27 L/(molmin) ??????k?298.2K?=?61?L/(molmin)

?????????35????????kT2???????????Ea?

????=35.00? ?0=2300?scm-1

V????=10.00mL [????]=0.0100 mol/L VNaOH=10.00mL[NaOH]= 0.0100 mol/L

?????m2=9.45

k2 =1/(mc0)=1/(9.450.0100) =10.58 L/(molmin) ??????k?308.2K?=?102?L/(molmin)

b.??????????? ?m1?1 , m2?1

k2c0k1c0?

k2m1

?k1m2

?ln

k2Ea11?(?) k1RT1T2

?ln

m1Ea11

?(?) m2RT1T2

m2T1?T2

?

m1T2?T1

Ea?R?ln

?

18.98308?298

?

9.45308?298

?53.21kJ/mol?8.314?ln

???????????

???????

??????????????????????

lgk??1780T-1?0.00754T?4.53

??T?298.2K??

lgk 1??1780298.2?0.00754298.2?4.53?0.809

?298.2K?????????k 1?6.442 L/(molmin) ???????????????????

5.27?6.442

?100%??18.2%

6.442

??T?308.2K??

lgk 2??1780308.2?0.00754308.2?4.53?1.078

?308.2K?????????k 2?11.967 L/(molmin) ?????????????????????ln

10.58?11.967

?100%??11.6%

11.967

k2Ea11?(?) k1RT1T2

lg

k2

?lgk2?lgk1?0.269 k1

k2

?10?0.269?1.858 k1

ln

k2

?ln1.858?0.619 k1

k2T1?T2

?

k1T2?T1

308?298 308?298

Ea?R?ln

?8.314?0.619??47.3kJ/mol

?????

53.2?47.3

?100%?12.4%

47.3

???????

?????????????????NaOH???????????25??35??????????????????????5.27 L/(molmin)? 10.58 L/(molmin)???????????????-18.2%?-11.6%???????????????53.2 kJ/mol?????????????12.4%?

?????????????????????????????? ???????????????k???????????????????????????????????????0.2??????????????????

?????????????????????????NaOH?????????????????0.0200mol/L????????????????????????????????????????????????????????????????

?????????????????????????????????????????????????????????????????????????????????????????????

??????NaOH?????????CO2???NaOH?????????????????



???????????OH?CO32????????????????????????????????

????????????????????????????????

????????????????????????(a= b) ????????????????????????????????????????????a?b??????????,???????????????????????????

??a<b (1<ba?115) ??N aOH ????????????CH3COOC2H5???N aOH???????????????????????????a?b???????????????????????, ????????????????????

??a> b (1<ab?114) ?????????N aOH???????????CH3COOC2H5??????????????????????????????????????????????a> b???????????

???????

????????????????CH3COOC2H5?NaOH?????????????

????????k?????????kT+10?/kT=2~4??????????????????????????????????????????????????????????????????????????????????

????CH3COOC2H5?NaOH????????????????????k??

????k?

???tb(a?x)1

lna (a???????????????k???? x?0

t(a?b)a(b?x)?0???

????)?X?????????

? ?NaOH??????a?CH3COOC2H5?????b??a?b????

NaOH ?CH3CH3COONa?C2H5OH

t?0 a b00 t?t a?x b?x xx t??0b?a aa ????????????????????????: ?0?A1 a????A2 a??t?A1(a?x)?A2 x

A1?A2???????????NaOH?CH3COONa???????????

???t

a ?????????????x?0

?0???

? ?NaOH??????b?CH3COOC2H5?????a??a?b????

NaOH ?CH3COOC2H5 CH3COONa?C2H5OH

t?0 b a 00 t?t b?x a?xxx t?? b?a0 aa ????????????????????????: ?0?A1 b????A1(b?a )?A2 a??t?A1(b?x)?A2 x

???t

a ?????????????x?0

?0???

???????pH??????????????????????????

??

?????CH3COOC2H5?OH=CH3COO?C2H5OH?????????v=dx/dt=k(a-x)(b-x)?????????a=b???????????k=x/ta(a-x)??t?????pH????t???????OH-????????????????ct?OH-?=10pH-14??a-x=10pH-14?ka=[a-10pH-14]/[t10pH-14]??a-10pH-14?[t10pH-14????????????????m=ka??k=m/a?

???NaOH?CH3COOC2H5???????????????k??????

???????????????????????????????????????????

?

?????????NaOH?CH3COOC2H5??????0.0200 moldm3????????????????????????

??????

[1]?????.??????.??:???????,2001. [2]???.??????.??:???????,2007. [3]????.?????(???).???????,2008.

[4]???.??.??.??????????????????.????????.No14, 2001

??????????????????

????

????? ???????P? ????? ???_______________

???????????????????? ????? ???? ??????? ???????

1. ???????????????????????????? 2. ???????????????????????????? 3. ????????????????????????? ?????? ??????

A + B ? ?? ??A?B????????????a???????????

dx2

?1? ?k?a-x?

dt???x?t???????????1??????

?

? ?2? 1?x

k??

t?a(a?x)??

x

?t?????????????????????????????k?????????a?x

????????????????????????????????k? ???????????????????????

Edlnk

?a2 ?3? dTRT

???Ea????????????????????????????????k(T1)?k(T2)??????3?????????Ea?

Ea?ln

?T1T2? ?4? k(T2)

?R??T?T??k(T1)1??2

?????????????????????????

CH3COOC2H5?OH??CH3COO??C2H5OH

??????OH?????CH3COO????????????????????OH????????CH3COO

???????????????????????????????????????????????????????????????????????????????????????????

----

?0?A1a ?5? ???A2a ?6?

?t?A1(a?x)?A2x ?7?

???A1?A2???????????????????????????0??t???????t?????????????? ???5???7???

1

?

????????

??0??tx??????

??0

???(2)?????

???a ?8? ?

?t?

?????t?

1??0??t?????? ?9? ak?t?

?0??t

t

????????????????????????????????k?

???????????????k (T1)?k(T2)???????????Ea???????????????????????????????????

???????

?? DDS-llA?????1?????????1??????1??DJS-1?????1???????2?????1??100mL???1??20mL???3??0.2mL?????1?? ?? 0.0200mol/L?NaOH????????AR?????????????

??????

1. ???????????????????????????????????????????

???

2. ???????????????0.0200mol/L???????100mL????????????

??

?=924.54-1.168t-1.9510-3t2 ?10?

????t??????kg/m3???????????0.1762g? 3. ??

?1??0???????????30????????20mL0.200mol/L?NaOH??????????????20mLH2O??????????????????????????????????????????????10min????????????????????????????

?2??t????????????????????????????20mL0.200mol/L???????????????????????3??????????????????????????????????20mL0.200mol/LNaOH??????????10min?????????????????NaOH???????????????????????????????????20min???????

?3??????????40??????0??t?

?????????

???27.4??????101.78kPa?

2

T1=30.00?

?0=9.23? ?0=2.20103?s/cm a=0.01mol/L

?1 ??????????????????30.00??

??t/min 0

0.42 1.27 2.12 3.12 4.22 5.32 6.33 7.30 8.28 9.17 10.17 11.23 12.40 13.60 14.70

????t/?

9.25 9.10 8.87 8.67 8.48 8.31 8.16 7.98 7.87 7.73 7.64 7.54 7.45 7.35 7.23 7.18

?1 30.00??

? ~????/ t??

??0?t?/ t

0.310 0.283 0.264 0.240 0.218 0.201 0.197 0.186 0.181 0.173 0.166 0.159 0.152 0.147 0.139

???1??30.00?????0??t?????11.559min-1

t

?1/ak = 11.559min-1 k = 1 /?11.559 min-10.01mol/L? ???30??????????????8.65 Lmol-1min-1

3

t

=8.65 Lmol-1min-1

T2=40.00?

?0=10.68? ?0=2.54103?s/cm a=0.01mol/L

?2 ??????????????????40.00??

??t/min 0

1.25 2.45 3.50 4.97 6.07 7.03 8.10 9.18 10.57 11.68 12.95 14.05 15.05

????t/?

10.62 10.01 9.54 9.19 8.87 8.67 8.5 8.33 8.20 8.05 7.96 7.83 7.75 7.68

??0?t?/ t

0.536 0.465 0.426 0.364 0.331 0.310 0.290 0.270 0.249 0.233 0.220 0.209 0.199

?2 40.00??

? ~????/ t??

4

???2??40.00????0t?????6.850min-1

t

?1/ak = 6.850 mink = 1 /?6.850 min-10.01mol/L? ???40??????????????14.60 Lmol-1min-1

-1

t

=14.60 Lmol-1min-1

3. ????????????????

Ea?ln

?T1T2?k(T2)

??R???k(T1)?T2?T1?

k?303.15K?= 8.65 Lmol-1min-1 k?313.15K?= 14.60 Lmol-1min-1

Ea = ln?14.60 / 8.65?8.314?313.15303.15 / 10?

= 41315Jmol-1 =41.315kJmol-1

???????

1. ????

???????????????

?1?NaOH?????????????????????????

?2??????????NaOH ??????CO2??NaOH????? ?3???????????????????????????????? ?4?????????????????????????? 2. ????????????

?1? ?????????????????????

?2???NaOH???CH3COOC2H5???????????????????? ?3???????????????NaOH???????????CO2???? ?4????????????????????????????? ?5??????????????????????

5


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