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=(2×0.01835×26.50×39.10×10-3/0.6842)×100%=5.56% K2O%=K%×M (K2O)/ 2 M (K)=5.56%×92.20/(2×39.10)=6.56% 30. Ca2+ +EDTA→CaEDTA

n(Ca2+)=n (CaO)= mS·WCaO%/M (CaO)=n (E)=CV (E) WCaO%=CV (E)·M (CaO)/ mS

=0.02000×20.00×10-3×56.08/(0.5608×25.00/250.00) ×100%=40.00%

31. 钙指示剂:EDTA+Ca2+→CaEDTA

C(Ca)V水/ M(Ca)=C (EDTA) V1( EDTA) C(Ca)= C (EDTA) V( EDTA) M(Ca)/ V水

=0.01000×10×10-3×40.00×103/(100.00×10-3)=40.00mg/L

铬黑T: EDTA+Ca2+→CaEDTA

EDTA+Mg2+→MgEDTA

C (EDTA) V2( EDTA)= C(Ca)V水/ M(Ca)+ C(Mg)V水/ M(Mg) C(Mg)={ [C (EDTA) V2( EDTA)-C (EDTA) V1( EDTA)]/ V水}×M(Mg)

-33-3

={0.01000×(20.00-10.00)×10×24.31×10}/(100.00×10)=24.31mg/L

2+

32. BaCO3+2HCl→Ba+H2O+CO2 Ba2++EDTA→BaEDTA

[msω(BaCO3)/M(BaCO3)]×(50.00/250)=CV

ω(BaCO3)=250CV M(BaCO3)/50.00ms=250×0.01000×20.00×10-3×197.34/(50.00×0.1973) =100.0%

θ

33.(1)E=E+0.0592/2×lg [C2 (Ag+)/C(Cu2+)]

=(0.80-0.34)+0.0592/2×lg(0.12/0.1)=0.43V

(2)(-)Cu│Cu2+ (0.1mol/L) ‖Ag+ (0.1mol/L) │Ag(+)

(3)(-)Cu → Cu2+ + 2e (+)Ag+ + e → Ag Cu + 2Ag+ → Cu2+ + 2Ag

θ

34. 据φ=φ+(0.0592/1)×lgC(Ag+)

当C (NH3)=1mol/L,C ([Ag(NH3) 2]+)=1mol/L时,所求的电极为标准电极。 C (Ag+)= C ([Ag(NH3) 2]+)/(K稳·C2 (NH3))=1/(1.0×107)=1.0×10-7

θ

∴ φ([Ag(NH3) 2]+ /Ag )=φ ([Ag+/Ag )

θ

=φ(Ag+/Ag )+(0.0592/1)×lg C (Ag+)

=0.799+0.0592×lg(1.0×10-7)=0.385V 35. (1) (-) Cu CuSO4(0.01mol/L) AgNO3(C) Ag (+) (2) 负极 Cu → Cu2++2e 正极 Ag+ +e → Ag 电池 Cu + 2 Ag+ → Cu2++ 2Ag

θ

(3) 根据能斯特方程 E=0.46=E+(0.0592/2)lgC2(Ag+)/C(Cu2+) =0.80-0.34+(0.0592/2)×lg[C2(Ag+)/0.01] 得C(Ag+)=0.1mol/L

θθθ

(4) 根据ΔrGm=-nFE=-RT㏑K

θθ

㏑K= nFE/ (RT)=2×96484×(0.80-0.34)/(8.314×298)=35.8275

θ

K=3.6×1015

36. 电池反应 3H2+Cr2O72-+8H+→2Cr3++7H2O 负极反应 H2→2H++2e

正极反应 Cr2O72-+14+6e→2Cr3++7H2O

θθ

根据能斯特方程 E=E+(0.059/6)lgC(Cr2O72-)C8(H+)[p(H2)/p]3/C2(Cr3+) =1.33-0+(0.059/6)lg1×(10-3)×13/12 =1.094V

θθθ

lgK=nFE/2.303RT=nE/0.059=6×(1.33-0)/0.059=135.2542 θ

K=1.8×10135

37. (1) 因为 C (Na2S2O3)=m ( Na2S2O3·5H2O)/ M ( Na2S2O3·5H2O)·V

所以 m= 0.1×248.2×2=50g

(2) 因为Cr2O72-+6I-+14H+ → 2Cr3+ +3I2+7H2O 3I2+6S2O32- → 6I-+3S4O62-

则:n (1/6 K2Cr2O7) = n (Na2S2O3)

即: C (Na2S2O3)·V (Na2S2O3)×10-3 = m (K2Cr2O7) / M (1/6 K2Cr2O7) 所以C (Na2S2O3)=0.4903×(25.00/100.0)×103/ [(294.0/6)×24.95]

=0.1002 mol/L (3) 因为2Cu2++4I- → I2+2CuI I2+2 S2O32- →2I- +S4O62-

所以:Cu%= [C(Na2S2O3)·V (Na2S2O3)·M (Cu)×10-3/ W]×100%

=(0.1002×25.13×63.55×10-3/0.2000)×100%=80.01% 38. 2Cu2++4I-→2CuI+I2 I2+2S2O32-→2I-+S4O62-

n(Cu2+)= ms·ω(CuSO4·5H2O) / M (CuSO4·5H2O)=n (Na2SO3)=CV

ω(CuSO4·5H2O) =(CV/mS)·M=(0.1000×20.00×10-3/0.5050)×250.00×100%=99.01% 39. 5C2O42- + 2MnO4- +16H+ → 10CO2 + 2Mn2+ +8H2O (1/5) n=(1/5) m / M (Na2C2O4)=(1/2) CV m=(5/2)CVM=(5/2)×0.02000×25.00×103×134.0=0.1675g 40. H2C2O4+2NaOH → Na2C2O4+2H2O n草=msω/M=(1/2)CV ω= CV M/2ms=0.1011×22.60×10-3×126.0/2×0.1560=92.27%

2-++

41. 5C2O4+2MnO4+16H→10CO2+2Mn2++8H2O

CV=(2/5) n=(2/5) m/M m=(5/2)CVM=(5/2)×0.1000×20.00×10-3×40.00=0.2g 42. 2MnO4-+5C2O42-+16H+→2Mn2++10CO2+8H2O (1/2)CV=(1/5)m/M C=(2/5)m/(MV)=2×0.13534/(5×134.0×20.00×10-3)=0.02020mol/L 43. Cr2O72-+6I-+14H+→2Cr3++3I2+7H2O I2+2Na2S2O3→2NaI+Na2S4O6

m/M=(1/6)CV C=6m/(MV)=6×0.1471/(294.2×30.00×10-3)=0.1000mol/L

44. I2+2S2O32- → 2I+S4O62-

n(I2)=1/2 n(S2O32-)+3n(丙酮)

(CV)(I2)=1/2(CV)(S2O32-)+3(ms×丙酮%)/M丙酮

丙酮%=[(CV)(I2)—1/2(CV)(S2O32-)]/ 3 ms ×M丙酮×100%

=[(0.05000×50.00—1/2 ×0.1000×10.00) /( 3×0.1000 )] ×10-3×58.03×100% =38.69%

45. 5C2O42-+2 MnO4-+16H+→10CO2+ 2Mn2++8H2O

(1/5)nNa=(1/2)nK (1/5)m/M=(1/2)CV

C=(2/5)m/MV=(2/5)×0.1474/(134.0×22.00×10-3)=0.02000mol/L 46. 2Cu2++4I-→2CuI+I2 I2+2S2O32- →4I- +S4O62-

n(Cu2+)= msω(Cu2+)/M=n(Na2S2O3)=CV ω(Cu2+)= CV M/ms=0.1010×20.00×10-3×63.55/0.5135=25.00% 2+2-+3+3+

47. 6Fe+Cr2O7+14H→6 Fe+Cr+7H2O

(1/6)n(Fe2+)=n(K2Cr2O7) (1/6) msω(Fe 2+)/M(Fe)=CV ω(Fe 2+)=6CV M(Fe)/ ms=6×0.02020×19.80×10-3×55.85/1.0020=13.38% 48. 阴离子E=K'-(2.303RT/F)lg aF- 0.400=K'-(2.303RT/F)lg(msω/M)×(5/50)/(50/1000) 0.300=K'-(2.303RT/F)lg(1×1.00×10-3×10-3)/(50/1000) 0.400-0.300=-0.059 lg msω×(5/50)/ (1×1.00×10-3×10-3) ω=2.0×10-6=0.0002% 49. 根据: A=εbc

试样: 0.400=εL·×WMn%/(55.00×250/1000) 标样: 0.550=εL·1.00×10-6

WMn% = [0.400×55.00×250/1000/ (0.550×1.00)]×1.00×10-6×100%=0.00100% 50. 根据朗伯比尔定律 A=εLC 0.800=εL4

0.200=εLC C=(0.200/0.800)×4=1 μg/mL 51. 据A=lgI/I0=-lgT=εcL

甲:A=-lg0.65=0.187 乙:A=-lg0.42=0.377

据 A=-lg0.65=0.187=εc甲L

A=-lg0.42=0.377=εc乙L

则 c乙=( lg0.42/ lg0.65)×6.5×10-4=1.31×l0-3mol/L 52. 根据朗伯比尔定律 A=-lgT=εLC -lg0.60=εL6

-lg0.80=εLC C(Fe3+)=6 ×lg0.80/lg0.60=2.6μg/mL 53. A=εCL=εL ·msω/(MV)

ω=AVM/(εLms)=0.400×50.00×10-3×55.85/(1.0×104×0.5585)=2×10-4=0.02% A=-lgT=εCL 0.400×(1/2)=-lgT T=10-0.200=63.1%