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1 m m kg t s I A T K n mol I v cd SISI SI 10 1 SI molecular weight1 12 C 112 relative molecular mass of a substance g 1 mol dalton 12 C 112 SI x10-27 kg Da SI SI SI 10-1 deci d 10 deca da 10-2 centi c 10 2 hecto h 10-3 milli m 10 3 kilo k 10-6 micro µ 10 6 mega M 10-9 nano n 10 9 giga G pico p tera T femto f peta P atto a exa E
2 ph deflectional methodnull method precision accuracy
3 µ σ ± σ 68%± 2σ± 3σ 95%99.7% n x I i = 1n σ s s > σ 1.1.2n n 1 n s σ 100s RSDCV s 2 = V n µ µ σ
4 95% P = 0.05 µ ± σ s µφ = n 1t t µ %P = 0.05 t φ t φ t y abc y = f a, b, c,δy yab s y s a s b y = kab yab s y ys a as b b 4
5 1.1.8 y = ka n : F F o V 1 > V F o F 95% P = 0.05 F %P = 0.05 F φ 1 φ
6 F 0 F 0 F 95% F 0 > F 95% F t µ µ µ t t o t t o t 95%µ t o > t 95% t φφ = n t o t o t t φ φ = n 1 +n 2 2 t o t 1 95% t o > t 95% 6
7 Dixon x 1 x 2 Q o x min x max Q o Q 90%P = 0.10 Q Q o > Q 90% x 1 Q o Q %P = 0.10 Q n Q x y y x a b Y y x a b y y y a b
8 x i y i r r 1 < r < 1 r = 1 r = 1 r > r 1 r t o t t t φ = n 2 t o > t y x a b sa sb b ± tsbt : φ = n 2 y x y = f yy =ax+b y y y gnuplot y= hx 1 M.L.McGlashan J.C. Miller, J.N.Miller
9 AEx TD EIn TC 1-2-1d a b c d e f g h abcd efgh
10 a 1-2-1b 1-2-1b ml 10
11 e f ) 0.01 ml
12 h 1-2-1g P P µl
13 1-2-4 P P-2P-10 P-20P-100 P-200P-1000 P mm 23 mm 24 mm 36 mm P-2P
14 A B M Mg Mg Mg A-D Mg mg 0.1 mg 1 g 10 % 1 ± 0.1 g 0.1 mg g 14
15 W V W o W 1 W=W 1 W o W V 15
16 20 C 20 C 1-2-1a 1-2-1b c c V a g cm 3 t C b c 10 5 t C % Mw C V W V W ±10%0.1 mg c real C real C f C real 16
17 C real C f KIO C Pww% W d V s 17
18 1.2.5 P d P d C Mw dg ml 1 Pww % M HCl HNO H 2 SO H 3 PO CH 3 COOH NH HClO H 2 O ph ph H ph x ph RTF A B Nernst x s AgAgCl ph ph ph 18
19 1.2.7 T ph A ph ph 4 9 ph B ph HA HA H + + A K a
20 HA A C K a HA A logk a = pk a HA H 2 O H + + OH K w BOH BOH B + + OH HA BOH C A HA C B BOH A B )
21 HA C B = 0C A K a >> M 2 C A >> K a =OH HA αa = αc A H Ostwald C A << K a K a C A << M 2 OH C A = 10 6 M HCN K a = M1.2.19H + ph = ph 7 B H + B K a B H + B BOH C A = C B leveling effect K a HA C A C A BOH C A H + = C A OH = C B H + H 3 O + OH HCl ΔC B ph ΔpH logδc B C A > C B H + H 3 O + H 2 O H 2 O OH HA HA ΔHA= ΔA ΔC B ΔH + << ΔC B H ΔH + = ΔC B H 2 O ΔOH = ΔC B β 21
22 H HA A K a = H + C A H + H 3 O + H 2 O H 2 O OH ph pk a HA ph ph pk a ± 1 pk a 2 ph γ RTlnγ γ = 1 γ < 1 (r) Debye-HückelA M 1/2 25 Cz I i z i C i 0.1 M NaCl I 0.1 M0.1 M Na 2 SO 4 I
23 M I B M 1/2 m 1 NaCl = m Davies I γ K a < I pk a pk a I HA C HA MV HA ml A C A MV A ml NaH 2 PO 4 Na 2 HPO 4 ph 311 ph Henderson-Hasselbalch ph ph ph B C B MV B ml HA C HA MV HA ml 23
24 Na 2 HPO 4 + HCl CH 3 COONa + HClTris + HCl Tris H 2 NCCH 2 OH 3 B + H K a ph C B V B > C HA V HA ph ph ph HA C HA MV HA ml BOH (C B MV B ml) NaH 2 PO 4 + NaOH + NaOHNH 4 Cl + NaOHH 3 BO 3 + NaOH AH K a ph C HA V HA > C B V B ph ph ph + Na 2 HPO 4 MacIlvaine ph Na K + SO 4 2 NO 3 pk a 1-2-3Ca 2+ Fe 2+/ pk a pk a 2.15 H 3 PO HOOCCH 2 NH HOC(COOH)(CH 2 COOH) HOC(COOH)(CH 2 COOH)CH 2 COO CH 3 COOH 6.15 MES 6.40 HOC(COOH)(CH COO )
25 ph CA ph ph I pka ph [HA] [A ] NaCl ph ph H + C B pk a C A = 0.1 M ph ph logαc A C B = C A 2 phph eq H + OH pk a ph ph eq/ K a pk a < C A K a 25
26 ph eq2 = C A 2 pk a ph eq = OH ph C B = C A phph eq C A ph eq = pk W 2 = ph eq > K a >> [H + ] eq pk a HA 1 C A,1 K a,1 HA 2 C A,2 K a, pk a,1 << pk a,2 HA HA 1 26
27 C A,1 HA 2 pk a,1 pk a, H 2 A 2HA H 2 A A 2 H 2 A a b C A H 2 A BOH( C B ) a,b H 2 AHA A 2 C A K a,1 K a, H 2 A BOH (1.2.38) pk a,1 >> pk a,2 K a,1 H + >> K a,2 H K a,2 H C A,1 = C A,2 pk a,1 >> pk a,2 2HA H 2 A A 2 C A H 2 A HA ph ph In InH In ph
28 InH pk a ph ph ph pk a ph ph 7 ph 4 ph ph ph ph ph V ph
29 λ = nmλ = nm πnd I C M λ ελ M 1 cm 1 λaλ tλ Tλ Lambert-Beer Aλ C Aλλ λ max εε max ε max λ max π π* ε max > 2000-C=C-CO- ε max > 10000ε max > 100n π*-co-no 2 n ε max < 100 λ max ε max ΔE = hcλbohr 29
30 π n p ε max π π* n π*λ max σ π d* d σ*π* d d d ε max = mM = 1 cm ε max > λ(nm) log t C t F dCC
31 F F A F A = A = A t t = 0 t = W D 2 λ > 350 nm λ < 360 nm
32 NO nm Excel p TARE g 10 ml 32
33 W g 9 W 2 W 10 W W 0 90P = 0.10Dixon Dixon W W 0 n 10( )(s) c ml V ml 95%F 95% V 10.0 ml µl 200 µl 20 µl P-1000P-200P µl 1000 µl 1000 µl W g 9 W 2 W 0 3 W W 0 W W 0 90(P = 0.10) W W 0 n 10( )(s) coefficient of variation; 33
34 CV V ml% = 100V V o V o ; V o CV O µl CV P P P ph ph ph CLR + CAL ph F + CAL H 3 PO 4 ; Mw M f B 3L ph ph 4 MR 0.1 g 45 ml 50 ml25 PP 0.5 g 45 ml 50 ml25 34
35 !! 1.2 g 100 ml Fill-up P ml 10 ml 40 ml M NaOH M NaOH ml W mg 0.1 M NaOH f B H 3 PO 4 NaOH 0.1 M NaOH 1 ml = mg H 3 PO W wmg Pww% ph pk a,2 H 2 PO 4 pk a ph pk a,1 H 3 PO 4 pk a C A W (40 ml) ph pk a,3 HPO 4 2 pk a C A ΔpH ΔV B ΔV B ΔpH ph β ΔC B ΔpH ΔC B = C B f B ΔV B V t β V t ml 35
36 β C B f B ΔV B ΔpHV t ph ph ph pk a Excel ph etylenediamine tetraacetic acid, EDTA chelatometry EDTAH 4 Y H 4 Y H 3 Y H Y 2 HY 3 Y 4 Y 4 11 PtIV FeIIIY 4 Lewis H + Y 4 M n+ EDTA K MY,app K MY M n+ Y 4 α H Y t Y 4 EDTA K 1 pk 1 = 2.0K 2 pk 2 = 2.67K 3 pk 3 = 6.16K 4 pk 4 = α H ph K MY,app ph ph EBT
37 Mg 2+ EDTA logk MY 8.69 ph10 ph 11 Mg(OH) 2 Mg 2+ ph 1011 EBT Ca 2+ logk MY ph 13 ph NNMg 2+ Ca 2+ Mg 2+ Mg 2+ Ca 2+ ph 1213 Mg 2+ Ca 2+ EDTA ph H + Ca logα H ph Mg 2+ CaCO 3 Mw: ppm ppm = parts per million = M EDTA f E EDTA2Na2H 2 OMw g ml 6 Zn 25 6L 0.01 M f Mg MgCl 2 6H 2 OMw g mledta 25 EBT 0.1% 1:1 50mL 14 g 114 ml 200 ml; % 10 g ml25 10%NaOH 20 g ml25 NN K 2 SO ml 0.01 M 1.00 mlph 10 1 mlebt 5, M EDTA V E,t ml Mg 2+ EBT MgCl 2 37
38 ml 10% 1 ml10% 35 NN 0.05 g 0.01 M EDTA V E,Ca mlnn NN V E,t ml0.01 M EDTA f E 0.01 M f Mg EDTA CaCO M EDTA 1mL = mg CaCO 3 ppm= f E V E,t 1.00f Mg V E,Ca ml 0.01 M EDTA f E ppm = f E V E,Ca EDTA Mg 2+ Ca 2+ logk MY α H ph ph logk MY,app K MY,app C C L-ascorbic acid, AsAdehydroascorbate; DAsA AsA 2,6-2,6-dichlorophenolindophenol; DCIP 38
39 1.3.A1 AsA DAsA 1.3.A2 DCIP 2,6-dichloro-4-hydroxy-N-(4-hydroxyohenyl)-aniline DCIP DCIP AsA AsA DCIP 1.3.A3 DCIP AsA DCIP KIO 3 DCIP DCIP AsA IO IO 3 + 5e + 6H + 12 I 2 +3H 2 O 1.3.A4 6 6 IO 3 + 6e + 6H + I +3H 2 O 1.3.A5 3 M 4 IO 3 + 4e + Cl + 6H + ICl +3H 2 O AsA I 2 KIO 3 3AsA + KIO 3 3DAsA KI + 3H 2 O AsA 13KIO A6 1.3.A7 KI KIO 3 KI I 2 5KI + KIO 3 + 6H + 3I 2 + 6K + + 3H 2 O 1.3.A8 I 2 I 2 KI I 3 I 3 I 2 KIO 3 AsA 39
40 5% HPO 3 ; Mw %150g 2.85 L 25 2% 5% 40 ml 60 ml AsA 4mg100mL; 0.2 mm AsAC 6 H 8 O 6 ; Mw mg 2% 500 ml 100 ml AsA 6% KI KIMw g 100 ml 25 5 mm KIO 3 KIO 3 Mw g = W g 500 ml 5 mm KIO 3 W 25 f (KIO 3 ) = W mm KIO 3 5 mm KIO 3 20 ml 500 L 0.5% 0.5 g 100 ml mm DCIP DCIP-Na2H 2 OC 12 H 6 Cl 2 NNaO 2 2H 2 O Mw g 3 L ml AsA 20 ml 6% KI 1 ml mm KIO 3 VKIO 3 mlasa AsA C mgmlf KIO mm KIO 3 1 ml = = mg AsA 1.3.A8 C mgml = fKIO 3 VKIO A9 100 ml AsA 20 ml DCIP (DCIP 1mL AsA A [mgml]dcip V(DCIP) [ml] AmgmL = 20.0CVDCIP 1.3.A10 40
41 5% ml 5% 7.0 ml 8.0 ml d = ml V S mlv S DCIP ml AsA AsA 0.51 mg V S AsA mg100 ml AsA mg100 ml = AV S DCIP100dV S 1.3.A11 AsA DCIP AsA AsA I 2 AsA KIO 3 AsA sucrose glucose fructose (H 2 O 2 ) 41
42 glucose gluconic acid H 2 O 2 3,3,5,5 -(TMB) TMB π π* 0.20 mgml C 12 H 22 O 11 : Mw = g 500 ml 25 5 ml 0.1 mgml C 6 H 12 O 6 Mw = g 1000 ml 25 5 ml 0.1M ph M ph ml mg2000 U100 ml 0.1 M ph ml 45 mg 9 ml 0.1M ph TMB TMB2HClMw mg 9 ml 25 GPO 36 mg 90 ml 0.1M ph6.0 9 mltmb 9 ml 0.1M ph ml 25 42
43 20 ml 1 M H 2 SO ml H 2 SO 4 11 = 200 ml 1 M18 M)25 3 ml 0.1 mgml 0.2 mgml P O M H 2 SO ml 450 nm A r r > p.46 mg100 ml µ 43
44 glc suc O H 2 SO
45 Excel Office OK or AZ Q 0 = Max-MinMaxMin =data 2 data1max-min) data1data2 Max-Min or F4 Q Q 0 =AVERAGE=STDEV = AVERAGE STDEV = F 0 F = F F 0 F t t = t 0, t = t t 0 t t 0 t 0 45
46 R R r Memo 46
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