|
|
??????????????(???????)
????????????????
? ? ?
???????????????????????
?????????????????????????????????????????????????????????????????????????????????????????
??????????????????????????????????????????????????????????????????????????????????????
????????????????????????????? ?1? ?????? ?2? ???????? ?3? ?????????? ?4? ???????????? ?5? ????????????????
?6? ????99%?????????????????? ???1????????????? ?2????????????? ?3????????????? ?4?????????????? ?5????????
?6???????????????????
??????????????????????????
?? ?????????????????????????????????????????
????????????????????
?? ?????????????????????????????
??????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????
?????????39.16%?????????39.12%?39.15%?39.18%?????39.19%?39.24%?39.28%??????????????????????
???????????
?????E?????????????????d?????s??????????????????????????
?.??????????????????????3.5g?????????? ??0.042%?0.041%
??0.04199%?0.04201% .??????????????
???????????
??????????2????????????2?????????????2?????????????????????????????4????????????????????????
??? ? ?
????????????0.1mg?????????????0.1%?????????????
?????????m??
?????????????0.2mg ??
0.2?10?3?100%?0.1% m?0.2g
m
?????????0.2g?
?????????????????%???41.24?41.27?41.23?41.26??????????????????????
?: x?(
)
% = 41.25% ?????????
d1=-0.01% d2=+0.02% d3=-0.02% d4=+0.01%
d
?
?
i?1
n
din
?()% = 0.015% s?
?di2
i?1
n?1
?
(0.01)2?(0.02)2?(0.02)2?(0.01)2
4?1
%=0.018%
CV=x100%=41.25?100%=0.044%
?????????????%???????20.39?20.41?20.43???????s?????95%???????
??x=%=20.41% s=3
(0.02)2?(0.02)2
%=0.02% ????????95%?n=3??t=4.303
20.41?? ?=()% =(20.41?0.05)% ????Cl????6???????????35.2 mg.L-1?s=0.7 mg.L-1,?????
?
?90%??????????
??????????90%?n=6??t=2.015 ? ?=x?
2.015?0.7=(35.2)mg/L=(35.20.6)mg/L 6n
???Q??????????????????????90%? ?1?24.26?24.50?24.73?24.63? ?2?6.400?6.416?6.222?6.408? ?3?31.50?31.68?31.54?31.82?
???1??????????24.26?24.50?24.63?24.73
x2?x1????24.26Q??=n1=24.73?24.26=0.51
????n=4??Q0.90=0.76 Q???Q0.90? ?24.26????? ?2??????????6.222?6.400?6.408?6.416
x2?x1????6.222 Q??=xn?x1=6.416?6.222=0.92 Q
??
?Q0.90?
?6.222???
?3??????????31.50?31.54?31.68?31.82
xn?xn?131.82?31.68
????31.82Q??=xn?x1=31.82?31.50=0.44Q
??
?Q0.90?
?31.82?????
???????P2O5?????%???????8.44?8.32?8.45?8.52?8.69?8.38 ??Grubbs??Q??????????????????????d?????s?????90%?99%??????????
???????????? 8.32?8.38?8.44?8.45?8.52?8.69?????xn ?1? ?Grubbs?????8.69????
??????? x=8.47% s=0.13%
xn?xG??=s=0.13=1.69
??2-3?????95%?n=6?, G?=1.82
G???G?, ?8.69%????? ?2? ?Q????
Q?? ==8.69?8.32=0.46
n1
??2-4?n=6?, Q0.90=0.56 Q???Q? ?8.69%?????????????????? ?3? x?( d?(
xn?xn?1
8.44?8.32?8.45?8.52?8.69?8.38)
)%=8.47%
6
0.03?0.15?0.02?0.05?0.22?0.09
)%=0.09%
6
s=
(0.03)2?(0.15)2?(0.02)2?(0.05)2?(0.22)2?(0.09)2
%=0.13%
?4? ??2-2?????90%?n=6??t=2.015
?? ?=?8.47
?=?8.470.11?% 6
?????????99%??? ?=?8.47
?%=?8.470.21?% 6
????????????0.123%??????????????????%??0.112?0.118?0.115?0.119????????????????????95%?
???????????????x=0.116%s=0.0032%
x??
t=
s
n=
0.116?0.1230.0032
4= 4.38
??2-2??t( 0.95, n=4)=3.18t???t? ????????????????? ????????????????
????n1=6 x1=71.26% s1=0.13% ???: n2=9 x2=71.38% s2=0.11% ???????????????
??F??=s2
?
2s?
2
??
2=1.40??2-5?F??3.69 =?0.11?
F???F? ?????????????
x1?x2
????t?????t=
s?
n1n2
n1?n2
s?=t =
(n1?1)s12?(n2?1)s22
=n1?n2?271.26?71.38
(6?1)?(0.13)2?(9?1)?(0.11)2
%=0.12 % 6?9
= 1.90
??2-2?f = n1+n2-2 = 6+9-2 = 13 , ???95 %?t??2.20 t???t?????????????
???????????????????%?? ???? ???4.08?4.03?3.94?3.90?3.96?3.99 ???? ???3.98?3.92?3.90?3.97?3.94 ?????????????????? ????????????
SI=0.065% SII=0.033%F=S2=(0.033)2=3.88
???2-5?F??6.26F???F? ???????????????? 10. ?????????????
?1?0.0251 ?2?0.2180 ?3?1.810 ?4?pH=2.50 ??(1) 3? (2) 4? (3) 2? (4) 2? 11.?????????????????
?1?2.1870.854 + 9.610 - 0.03260.00814? ?2?51.38/?8.7090.09460??
-5
-5
S?2
(0.065)2
?3?0.005164?136.6;
?8?8
?4?1.5?10?6.1?10?
3.3?10?6
???1???=1.868+0.000096+0.000265
=1.868
?2???=62.36 ?3???=705.2?4???=1.710
-5
??? ????
? ? ?
1????????????????????
??????????????????????????????????????????????????????????????????????????????
??????????????
??? ????????????
?????
1 ?????????????????????
?????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????
2 ???????????????????????????
?1??????? ?????????????????
?2????????? ????????????
?3??????????????????????????????
?4????????????? ???????????????????
?5?????????????????????????????????????
?6?????99%??????????????????
???????????????????????
3 ????????????????????????
????????????????????????????????????????
4 ??????????????????
??????????????????????????????????????????????????????????
5 ???????39.16%????????39.12%?39.15%?39.18%?????39.19%?39.24%?39.28%??????????????????????
???????????????????????????????
x1 = (39.12+39.15+39.18)3 =39.15(%)x2 = (39.19?39.24?39.28) 3 = 39.24(%) E1=39.15?39.16 =-0.01(%) E2=39.24?39.16 = 0.08(%)
6 ???????????????????????3.5 g?????????? ??0.042%?0.041% ??0.04199%?0.04201% ?????????????? ????????????????????????????????????
??? ????
?????
1? ????????????????????
?: ???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????
2? ?????????????????????
?: ????????99.9%?????????????????????????????
3????????????????
?:?????????????????????????????(stoichiometric point, sp)??????????????????(end point, ed )?
4????????????????????????????????
H2SO4, KOH, KMnO4, K2Cr2O7, KIO3, Na2S2O3?5H2O
?: K2Cr2O7, KIO3 ?????????????????????????????
5???????????????????????
?: ?????????????,?????.??????????????????????????????????????????
6??????????????????????????????
?: ???????????????????????????????????
7???H2C2O4?2H2O?????????????????????NaOH?????????????????
???????H2C2O4?2H2O?????????????????????????NaOH???????NaOH???????
8?????????????????????????????
?:?????????????????????????????????
? ?0.1000mol?L-1NaOH?????H2C2O4????.
?: H2C2O4 + 2NaOH = Na2C2O4 + 2H2O
??? ?????
?????41
1. ????????????????????
??????????????????????????????????????????????????????????
2. ??????????H2PO4-?NH4+?HPO42-?HCO3-?H2O????
??HPO42-, NH3 , PO43- , CO32- , OH- , C6H5O-
3. ??????????H2PO4-?HC2O4-?HPO42-?HCO3-?H2O?C2H5OH? ??H3PO4?H2C2O4?H2PO4-?H2CO3?H3O+?C2H5OH2+
4????????????????
HOAc?NH4+?F-?(CH2)6N4H+?H2PO4-?CN-, OAc-?HCO3-?H3PO4?(CH2)6N4?NH3?HCN?HF?CO3-
??HOAc?OAc-?NH4+?NH3?F-?HF?(CH2)6N4H+?(CH2)6N4?H2PO4- ?H3PO4?CN-?HCN,?HCO3-?CO3-
5. ????????????????????????????????????????????
???????????????????H3PO4?HF?HOAc?(CH2)6N4H+?HCN?NH4+?HCO3-
???????????????????CO32- ?NH3?CN-? (CH2)6N4?OAc-?F-?H2PO4-
6. HCl??HOAc???,?1mol?L-1HCl?1 mol?L-1HOAc???, ???[H3O+]??? ????NaOH?????????????
??1mol?L-1HCl??[H3O+]??, ??NaOH?????????HCl?????, ????, HOAc?????, ??????[H3O+]; HOAc??NaOH?, HOAc???????????????.?
7??????????????????(1) NH3?H2O; (2) NaHCO3?(3) Na2CO3??? NH3?H2O[H+]+[NH4+] = [OH-]
NaHCO3 [H+]+[H2CO3] = [CO3-]+[OH-]
Na2CO3 [HCO3-]+[H+]+2[H2CO3] = [OH-]
8. ?????????????????
(1)NH4HCO3?(2) (NH4)2HPO4?(3) NH4H2PO4?
??NH4HCO3[H+]+[H2CO3] = [NH3]+[CO32-]+[OH-]
(NH4)2HPO4 [H+]+[H2PO4-]+2[ H3PO4] = [NH3]+[PO43-]+[OH-]
NH4H2PO4 [H+]+ [ H3PO4] = [NH3]+2[PO43-]+[OH-]+ [HPO42-]
9. ????????????????????????pH????????????????(?????(pH?2.0 ????(??pH?12.0).?????
?: ?????????????????????????????????.???????????????????pH???. ????????????????? (pH?2.0 ????(??pH?12.0),?????0.01 mol?L-1???????0.01 mol?L-1????.
10. ???????,???????:
?1?1.0 mol?L-1?HOAc+ 1.0mol?L-1?NaOAc?
?2?1.0 mol?L-1?HOAc+ 0.01mol?L-1?NaOAc?
?3?0.0 1mol?L-1?HOAc+ 1.0mol?L-1?NaOAc.
????????????????????????? ????????????, ???????????????
?: (1)????????????????1, ????, ?????????, ???????????pH????; (2) ????????????????100, ?????(NaOAc)???, ????????, ?????, ?(3) ????????????????0.01, ?????(HOAc)???, ????????, ?????
11????pH?3????????????????????(????pKa)? HOAc(4.74)???(3.74)?????(2.86)?????(1.30)???(9.95)?
????pH?pKa?????C2HClCOOH?C2HClCOO-??pH?3????????
12. ??????pH=7.0??7.0???7.0?????
NH4NO3?NH4OAc?Na2SO4???????H2O?
??NH4NO3??pH?7.0?NH4+ ?pKa=10-9.26???; NH4OAc??pH=7.0???pKa(NH4+)?pKb(OAc-); Na2SO4 ??pH=7.0 , ?????????; ??????H2O?pH?7.0?????????H2O ????C02????pH=5.6?
?????4?2
1. ?????????????????? ?????????
???????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????????
2??????????????????
???????????????????????????????????pH?????????????????????????pH?
3????????????????????pH??? ?43?????????????????????? ???? ???????
??????????????pH=pKHin1?????????????2?pH????43??????????????????????????????????????????????????????pH?2.4~4.4????3.1~4.4????????????????pH?6.4~8.4??????????6.8~8.0?????????????????
4??????????????????????????????????????????
(1) CH2ClCOOH?HF??????????(2) CCl3COOH??????????????? ???1?CH2ClCOOH?HF???????pKa???2.86?3.46?9.95?
CH2ClCOOH?HF?????cKa?10-8???????????NaOH?????????????????????????cKa?10-8????????????
?????????pKb???8.04, 9.34, ???????????????cKb?10-8???????????HCl????????????????????????????????????????2?CCl3COOH????????pKa???0.64?4.21??????cKa?10-8???????????NaOH?????????????????
?????????????pKb???8.77?8.85?????cKb?10-8??????????????????????
5. ?????????????????? ????,?????????
NaF. NaOAc, ????, ??(C6H5ONa), ????(NH2OH?HCl)
?: ?????????0.1 mol?L-1, NaF ?Kb=10-14/(3.210-4) =3.110-11, cKb?10-8,????????????; NaOAc? Kb=10-14/(1.810-5) = 5.610-10, cKb?10-8,????????????; ??(C6H5ONa) Kb=10-14/(1.110-10) = 9.110-5, cKb?10-8, ???????????, ???????; ????(NH2OH?HCl) ? Ka=10-14/(9.110-9) =1.110-6, cKa?10-8, ???????????, ??????.
6??NaOH?????????????????????? ???????????????
H2S04?H2S03?H2C204?H2C03?H3P04
????????cKa?10-8?cKa1/cKa2?104????????????????????, ??H2S03?H3P04??????0.1mol/L???????????????????????
??? ???
H2S04 1 ???????
H2S03 2 SP1???, SP2??
H2C204 1 ??
H2C03 1 ??
H3P04 2 SP1???, SP2??
7. ?????????Ka1/Ka2?????????????????H2C2O4, ???, ?????,?????
?: H2C2O4?Ka1/Ka2=5.910-2/ 6.410-5= 9.2102?104, ??????; ????pKa=2.36?4???????; ???????pKa= 4.08?4(?P80)???4-7???pH2.86~4.72?????????????4-8????????????????Ka1/Ka2=6.410-5/ 2.710-6 = 2.4101?104, ??????.
8????NaOH?????????????????????? ??????
???????pKa?4.74????cKa?10-8???????????NaOH????????????pKa?9.24?????cKa?10-8????????????NaOH?????????
9????HCI??????????????????????? ??????
????????????B4O72- + 5H2O = 2H2BO3- + 2H3BO3 H2BO3-?H3BO3??????H2BO3-?pKb=14?9.24 = 4.76?????????????cKb?10-8???????????HCl????????????????????pKb=14?3.74=10.26?Kb???????cKb?10-8????????????HCl?????????
10.???????????????????????,????????????.
(1) 0.1mol?L-1HCl + 0.1 mol?L-1H3BO3; (2) 0.5 mol?L-1H3PO4 + 0.5 mol?L-1H2SO4
?: (1) ????pKa?9.24, ??, ??????HCl. (2) ?H3PO4?pKa1= 2.12, pKa2 =7.20, Ka1/Ka2?104, H2SO4?pKa2 = 1.99, ?????, ?????????????????????????????, ??????????????????, ????????????????????, ???????????????????.
11. ???????????????????????????????????????g?mL-1???? ?1?NaOH + NH3?H2O??2?NaOH + Na2CO3.
???1?NaOH????KNH3?H2O=1.810-5???HCl???????????????????????????V1???????????????????V2???????
w(NaOH) = c(HCl)V1(HCl)M(NaOH) 10-3/V???
w(NH3?H2O) = c(HCl)V2(HCl)M(NH3?H2O) 10-3/V???
(2) NaOH????K CO32 -=1.810-4, ??HCl??????????????1?????????????????????V1???????????????????V2???????
?????4?3
???????????????
?????????
??? 1??????????????????????????????????????????????????????????????????????????????????????????????????????????????
??????????????????????????????????????????????????????????
2????????????????????????????????????????HNO3????????????????????????????????????????????????????????????????????
??????????????????????????????????????? 3??????????????????????????
??????HNO3 ?????H3PO4? ???HCl? ???HNO3 ????HF? 4?????????????????????????????? ??? ??????Na2O2??????????? ??????????????? ?? ???????????? ????????????????
5????????Fe?Ni?Mg????????????????
???NaOH?????Fe?Ni?Mg??????????Zn?????
6????????SiO2????????Fe?Al?Ca?Mg?Ti??????????????????
???????SiO2???????????KOH?????????????????K2SiO3???????????????Fe?Al?Ca?Mg?Ti??????HF???????Si?SiF4???????????Fe?Al?Ca?Mg?Ti???? 7?????????????????????
???????????????????????????????????????????????????????????????????????????????? 8????????????????????C? a??????????????? b???????????? c?????????? d??????????
9?????????????????
?????????????????????????????????? 10?????????0.01?????????????0.1%?????????????????
0.02
V100%?0.1% V?20ml
11???????????0.001mg??????????1???????????
0.002
S1000?1 S?2mg
12???????????????????????????
a????? ???????????
b???????????????????????????????????????
???
c???????????????????? ??????
e?????98%????????????EDTA????? ????????????? f????????????????????????
g??????SiO2???????????? ??????????? h???????? ???????????
13?????????????
0.072 (2?)36.080 (5?) 4.410-3 (2?) 6.0231028 (4?) 100 (3?) 998 (3?????) 1000.00 (6?)1.0103 (2?)PH=5.2??[H+] (1?)
14?????????????????????????0.0520g???????????96.24%??????????????
????????????0.0520g??????????????????????????????????????????96.2%?
15??0.0089g BaSO4???Ba??????????????????????
0.59??0.5884
1
16????????????CaSO42 H2O????????????0.2000g?????????
?0.1mg??????????????????
0.20009.01
145.10.2000 100%= 6.21%
??????????0.01%??????????????????
17?????0.02000molL-1 K2Cr2O7??500ml??????????0.1mg?????????0.1%????K2Cr2O7????????????
?????0.1mg??????????????0.1%?????????0.2g????500mL0.02000 molL-1 K2Cr2O7, ????
294.2
m?K2Cr2O7?=0.020001000 500=2.942g
???????0.2g???????????????????????
18??????????????????KHC8H4O4?M=204.23gmol-1??????(H2C2O42H2O?M=126.07gmol-1)????????????????????????? ????????????????????????????
19????Na2CO3??HCl??????????HCl??????????????????????
mNaCO10002
?CHCl=MNaCO ?
22VHCl1
a????????????????HCl??????????????
????VHCl????? CHCl???
b???Na2CO3???????0.1834g???????0.1824g
?M?Na2CO3??????????CHCl???
c???HCl???????????????HCl????????
?????????HCl??????????VHCl?????CHCl??? d?????Na2CO3???????????50mL???
?????????Na2CO3??????????????????? e???????????????Ha??????????
????VHCl?????CHCl??? f????????HCl?? ????VHCl?????CHCl??? g???Na2CO3????????????????????? h???HCl??????
??????HCl??????????HCl???????????CHCl??????????????
20????HCl?????????Na2CO3??????12??????????????????????
CHCl?VHCl?
SMNa2CO31000
?
1
2100%
?Na2CO3%=
????????a?b?c?d?e?f???????????12??????d?g????h?????????????
21???H2C2O42H2O???????????????????????????NaOH????????????????????? ?????
mH2C2O4?2H2O
CNaOH?
MH2C2O4?2H2O
?1000?
21
VNaOH
??????H2C2O4????????H2C2O42H2O?????NaOH???H+????????VNaOH?????CNaOH???
22??6.00g NaH2PO4?8.197g Na3PO4???????????????2.500molL-1HCl 40.0mL????????????????
2.50040.06.00
n?NaH2PO4?=119.9 =0.0500 moln?HCl?=1000 =0.100 mol
8.197
n?Na3PO4?=163.9=0.0500 mol
???????n?Na2HPO4?=0.0500 +0.0500=0.1000mol?n?HCl?=0.100 mol????n(NaH2PO4)=0.1000mol?NaH2PO4??????
????????
1?????????????????????rH?rHSO4?rSO4??????
?
?
2?
??????????????????????????????????????????????????????????????????????????????????H+<SO42-<HSO4-??SO42-?2?????????????????????rH?rHSO4?rSO4?
?
?
2?
2???????????????????????Kca1?Kca2???????????????h????K0a1?K0a2???????? ??K
ca1
?
[H?][HC2O4]10??Ka
1
[H2C2O4]rH?rHSO?
4
K
c
a2
?
2?
[H?][C2O4]
[HC2O4]
?
?K
a2
rHCO?
2
4
rH?rcO2?
2
4
????????????????????????????????????????????
2??
???????Kca1?Kca2??????rHC2O4< rC2O4< rHC2O4???Kca1??????Kca2
????????Kca1?Kca2?????????????????????????????????K0a1?K0a2?????
3????????????????????????? ?1?C?molL-1?NH4HCO3
MBE?[NH3]+[NH4+]=CCBE:[NH4+]+[H+]=[OH-]+[HCO3-]+2[CO32-]]
[H2CO3] + [HCO3-]+[CO32-]=C PBE: [H+]=[OH-]+[NH3]+[CO32-]-[H2CO3] ?2?C(mol?L?1)NH4F
?[NH4?]?[NH3]?C????
MBE:? CBE:[NH]?[H]?[OH]?[F] 4?
?[HF]?[F]?C
PBE: [H+]=[OH-]+[NH3]-[HF] ?3?C(mol?L?1)NaNH4HPO4
?[Na?]?C?
MBE:?[NH3]?[NH?4]?C
?[HPO]?[HPO?]?[PO3?]?[HPO2?]?C
2444?34
??2?3?
CBE:[Na?]?[NH4]?[H?]?[OH?]?[H2PO4]?2[HPO4]?3[PO4]
3??PBE:[H?]?[OH?]?[NH3]?[PO4]?[H2PO4]?2[H3PO4]
?4?C(mol?L?1)NaNH4HPO4
?
?[NH3]?[NH4]?CMBE:??2?3?
?[H3PO4]?[H2PO4]?[HPO4]?[PO4]?C
??2?3?
CBE:[NH4]?[H?]?[OH?]?[H2PO4]?2[HPO4]?3[PO4]
2?3?
PBE:[H?]?[OH?]?[NH3]?[HPO4]?2[PO4]?[H3PO4]
?5? C1(mol?L?1)NH3?C2(mol?L?1)NaOH
?
?[NH3]?[NH4]?C1
MBE:??
?[Na]?C2
?
PBE:[H?]?[OH?]?[NH4]?C2
?
CBE:[Na?]?[NH4]?[H?]?[OH?]
?6?C1(mol?L?1)HAc?C2(mol?L?1)H3BO3
?[HAc]?[Ac?]?C1????
CBE:[H]?[OH]?[Ac]?[HBO] MBE:?23?
?[H3BO3]?[H2BO3]?C2
?
PBE:[H?]?[OH?]?[Ac?]?[H2BO3]
?7?C1(mol?L?1)H3PO4?C2(mol?L?1)HCOOH
?2?3?
?[H3PO4]?[H2PO4]?[HPO4]?[PO4]?C1
MBE:? ?
[HCOOH]?[HCOO]?C2?
?2?3?
CBE:[H?]?[OH?]?[HCOO?]?[H2PO4]?2[HPO4]?3[PO4] ?2?3?PBE:[H?]?[OH?]?[H2PO4]?2[HPO4]?3[PO4]?[HCOO?]
?8?C1(mol?L?1)NaH2PO4+C2(mol?L?1)HCl
?2?3?
?[H3PO4]?[H2PO4]?[HPO4]?[PO4]?C1?
MBE:?[Cl?]?C2
?[Na?]?C
1?
?2?3?
CBE:[H?]?[Na?]?[OH?]?[Cl?]?[H2PO4]?2[HPO4]?3[PO4]
2?3?PBE:[H?]?[OH?]?[HPO4]?2[PO4]?[H3PO4]?C2
?9?C(mol?L?1) (NH4)2CO3
?
?[NH3]?[NH4]?2CMBE:??2?
[HCO]?[HCO]?[CO]?C2333?
??2?
CBE:[NH4]?[H?]?[OH?]?[HCO3]?2[CO3]
?
PBE:[H?]?[OH?]?[NH3]?[HCO3]?2[H2CO3]
?10?C(mol?L?1)HAC?C2(mol?L?1)NaAC
????????????????????
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发表于 2019-9-13 23:46:11