1.1. 1.1.1. 1.1.1.1. m m kg t s I A T K n mol I v cd SISI SI 10 1 SI 1-1-1 molecular weight1 12 C 112 relative molecular mass of a substance g 1 mol dalton 12 C 112 SI 1 1.6605655x10-27 kg Da 1-1-1 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 10-12 pico p 10 12 tera T 10-15 femto f 10 15 peta P 10-18 atto a 10 18 exa E 1.1.1.2. 1
ph 1-1-2 1.1.1.3. deflectional methodnull method 1.1.2. precision accuracy 1-1-1 1-1-1 1.1.3. 1.1.3.1. 2
1.1.3.2. 1.1.3.3. 1.1.1 1-1-2 µ σ ± σ 68%± 2σ± 3σ 95%99.7% n x I i = 1n σ s 1-1-2 1.1.2 s > σ 1.1.2n n 1 n s σ 100s RSDCV s 2 = V 1.1.3.4. n µ µ σ 1.1.3 3
95% P = 0.05 µ ±1.96 1.1.4 1.1.3σ s µφ = n 1t 1-1-3 t µ 1.1.5 1-1-3 95%P = 0.05 t φ 1 2 3 4 5 6 7 8 9 10 t 12.71 4.303 3.182 2.766 2.571 2.447 2.365 2.306 2.262 2.228 φ 11 12 13 14 15 16 17 18 19 20 t 2.201 2.179 2.160 2.145 2.131 2.120 2.110 2.101 2.093 2.086 1.1.3.5. y abc y = f a, b, c,δy 1.1.6 yab s y s a s b 1.1.7 y = kab yab s y ys a as b b 4
1.1.8 y = ka n 1.1.9 : 1.1.10 1.1.4. 1.1.4.1. F F o V 1 > V 2 1.1.11 F o F 95% P = 0.05 F 1-1-4 1-1-4 95%P = 0.05 F φ 1 φ 2 1 2 3 4 5 6 7 8 9 10 1 161 200 216 225 230 234 237 239 241 242 2 18.5 19.0 19.2 19.2 19.3 19.3 19.4 19.4 19.4 19.4 3 10.1 9.55 8.28 9.12 9.01 8.94 8.89 8.85 8.81 8.79 4 7.71 6.94 6.59 6.39 6.26 6.16 6.09 6.04 6.00 5.96 5 6.61 5.79 5.41 5.19 5.05 4.95 4.88 4.82 4.77 4.74 6 5.99 5.14 4.76 4.53 4.39 4.28 4.21 4.15 4.10 4.06 7 5.59 4.74 4.35 4.12 3.97 3.87 3.79 3.73 3.68 3.64 8 5.32 4.46 4.07 3.84 3.69 3.58 3.50 3.44 3.39 3.35 9 5.12 4.26 3.86 3.63 3.48 3.37 3.29 3.23 3.18 3.14 10 4.96 4.10 3.71 3.48 3.33 3.22 3.14 3.07 3.02 2.98 5
1.1.11 F 0 F 0 F 95% F 0 > F 95% F 1.1.4.2. t µ µ µ t 1.1.5 1.1.12 1.1.12 t o 1-1-3 t t o t 95%µ t o > t 95% t φφ = n 1 1.1.4.1. 1.1.13 t o 1.1.12 1.1.14 t o 1-1-3 t t φ φ = n 1 +n 2 2 t o t 1 95% t o > t 95% 6
1.1.4.3. Dixon x 1 x 2 Q o 1.1.15 x min x max Q o Q 90%P = 0.10 Q 1-1-5 Q o > Q 90% x 1 Q o Q 1-1-5 90%P = 0.10 Q n 3 4 5 6 7 8 9 10 Q 0.94 0.76 0.64 0.56 0.51 0.47 0.44 0.41 1.1.5. 1.1.4. x y 1.1.16 y x a b Y y x a b y y y a b 1.1.17 1.1.18 7
x i y i r 1.1.19 r 1 < r < 1 r = 1 r = 1 r > 0.995 r 1 r t o t t 1.1.20 t φ = n 2 t o > t y x a b sa sb 1.1.21 1.1.22 1.1.5 b ± tsbt : φ = n 2 y x y = f yy =ax+b y y 1.1.3.5. y gnuplot y= hx 1 M.L.McGlashan 1981 2 1992 3 J.C. Miller, J.N.Miller 1991 8
1.2. 1.2.1. 1.2.1.1. 1-2-1 AEx TD EIn TC 1-2-1d a b c d e f g h 1-2-1 abcd efgh 1-2-2 1-2-2 9
1.2.1.2. 1-2-1a 1-2-1b 1-2-1b 1-2-3 1-2-3 5 ml 10
1.2.1.3. 1-2-1e 11015 3 1-2-1f ) 0.01 ml 1.2.1.4. 1.2.2.2.1.2.1.2. 11
1.1.3.5. 1.2.1.5 1.2.1.5. 1.2.2.3. 1-2-1h 1-2-1g 1.2.1.6. P P µl 1-2-4 13 1-2-4 12
1-2-4 P 1-2-5 P-2P-10 P-20P-100 P-200P-1000 P-5000 1 mm 23 mm 24 mm 36 mm 1 1-2-5P-2P-10 1-2-5 13
A B 1.2.2. 1.2.2.1. 1-2-6 M Mg Mg 1.1.1.3. Mg A-D Mg 1.2.2.2. 1-2-6 1.3.5. 0.1 mg 0.1 mg 1 g 10 % 1 ± 0.1 g 0.1 mg 1.0000 g 14
1.2.2.3. 1.2.1.5. 1.2.2.4. W V W o W 1 W=W 1 W o W V 15
20 C 20 C 1-2-1a 1-2-1b c c V 1.2.1 1-2-1a g cm 3 t C 0 1 2 3 4 5 6 7 8 9 10 0.99970 0.99961 0.99949 0.99938 0.99924 0.99910 0.99894 0.99877 0.99860 0.99841 20 0.99820 0.99799 0.99777 0.99754 0.99730 0.99704 0.99678 0.99651 0.99623 0.99594 1-2-1b c 10 5 t C 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 14 197 198 199 200 201 203 204 205 206 207 15 209 210 211 213 214 215 216 218 219 221 16 222 223 225 226 228 229 230 232 233 235 17 236 238 239 241 242 243 245 247 248 250 18 252 253 255 257 258 260 261 263 265 267 19 268 270 272 273 275 277 279 280 282 284 20 286 288 290 291 293 295 297 299 301 303 21 305 307 308 310 312 314 316 318 320 322 22 324 326 328 330 333 335 338 339 341 343 23 345 347 349 352 353 356 358 360 363 365 24 367 369 371 374 376 378 381 383 385 387 25 390 392 394 397 399 402 404 406 409 411 1.2.3. 1.2.3.1. 1.2.2.2. 100% Mw C V W 1.2.2 V W ±10%0.1 mg.1.2.2.2.c real C real C f 1.2.3 C real 16
C real C f KIO 3 1.2.3.2. 1.2.2.2.1.2.1.2. 1.2.1.4. 1.2.3.3. C Pww% W 1.2.2 1.2.4 d V s 17
1.2.5 P d 1-2-2 P d 1-2-2 15 C Mw dg ml 1 Pww % M HCl 36.47 1.19 37 12 HNO 3 63.02 1.42 70 16 H 2 SO 4 98.08 1.84 96 18 H 3 PO 4 98.00 1.70 85 15 CH 3 COOH 60.05 1.06 96 17 NH 3 17.03 0.90 28 15 HClO 4 100.47 1.55 60 9 H 2 O 2 34.01 1 30 9 1.2.4. ph 1.2.4.1. ph H + 1.2.6 ph 1-2-7 x ph 1.2.7 RTF A B Nernst x s 1-2-7 AgAgCl ph ph 1.2.4.2. ph 18
1.2.7 T ph 7 1.2.7 A ph ph 4 9 ph 1.2.7 B ph 1-2-7 1.2.5. 1.2.5.1. HA HA H + + A 1.2.8 K a 1.2.9 19
HA A C 1.2.10 K a HA A 1.2.11 logk a = pk a 1.2.12 HA H 2 O H + + OH 1.2.13 K w BOH BOH B + + OH 1.2.14 HA BOH C A HA C B BOH A 1.2.15 B 1.2.16 1.2.17 1.2.11)1.2.15 1.2.131.2.16 1.2.17 1.2.18 20
HA C B = 0C A K a >> 10 12 M 2 C A >> K a 1.2.18=OH HA αa = αc A H + 1.2.181.2.11Ostwald 1.2.19 C A << K a K a C A << 10 12 M 2 OH 1.2.19 C A = 10 6 M HCN K a = 6.0 10 10 M1.2.19H + ph = 7.6 1.2.18 ph 7 B H + B K a B H + B BOH C A = C B leveling effect K a HA 1.2.18 C A C A 1.2.14 BOH C A 1.2.18H + = C A OH = C B H + H 3 O + OH 1.2.13 HCl 1.2.5.2. 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
1.2.20 1.2.18H + 1.2.20 1.2.21 1.2.21 HA A K a = H + C A H + H 3 O + H 2 O H 2 O OH 1.2.21 ph pk a HA ph 1.2.21 ph pk a ± 1 pk a 2 ph 1.2.5.3. γ1.2.10 RTlnγ γ = 1 γ < 1 (r) 1-2-8 1-2-8 1.2.22 Debye-HückelA 0.509 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 0.3 22
M 1.2.23 I - 1.2.24 B 25 3.291 10 9 M 1/2 m 1 NaCl = 4 10 10 m Davies 1.2.25 I γ 1.2.11 K a 1.2.26 < I pk a pk a I 1.2.5.4. HA C HA MV HA ml A C A MV A ml NaH 2 PO 4 Na 2 HPO 4 ph 311 ph 1.2.27 Henderson-Hasselbalch ph ph ph B C B MV B ml HA C HA MV HA ml 23
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 1.2.28 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 1.2.29 ph ph ph + Na 2 HPO 4 MacIlvaine ph Na K + SO 4 2 NO 3 pk a 1-2-3Ca 2+ Fe 2+/3+ 1-2-3 pk a pk a 2.15 H 3 PO 4 2.35 + HOOCCH 2 NH 3 3.13 HOC(COOH)(CH 2 COOH) 2 4.76 HOC(COOH)(CH 2 COOH)CH 2 COO 24 4.76 CH 3 COOH 6.15 MES 6.40 HOC(COOH)(CH COO )
1.2.18 ph 1.2.1.5.1.2.2.3. CA ph ph I pka 1.2.26 ph [HA] [A ]1.2.12 1.2.15 1.2.181.2.23 NaCl ph 1.2.5.5. ph 1.2.18H + C B 1-2-9 pk a C A = 0.1 M 1.2.20 ph ph 1.2.19 logαc A C B = C A 2 phph eq2 3 11 H + OH 1.2.18 1.2.30 pk a ph ph eq/2 3 1.2.18 1.2.31 K a pk a < 01.2.31 C A K a 25
ph eq2 = C A 2 pk a ph eq2 11 1.2.18= OH 1.2.32 ph C B = C A phph eq 1.2.18 1 C A ph eq = pk W 2 = 7 1-2-9 ph eq > 7 1.2.18 K a >> [H + ] eq 1.2.33 1-2-9 pk a HA 1 C A,1 K a,1 HA 2 C A,2 K a,2 1.2.18 1.2.34 pk a,1 << pk a,2 HA 1 1.2.34HA 1 26
C A,1 HA 2 pk a,1 pk a,2 1.2.34 H 2 A 2HA H 2 A A 2 H 2 A 1.2.35a 1.2.35b C A 1.2.36 H 2 A BOH( C B ) 1.2.37 1.2.35a,b21.2.36H 2 AHA A 2 C A K a,1 K a,2 1.2.37 H 2 A BOH (1.2.38) pk a,1 >> pk a,2 K a,1 H + >> K a,2 H + 1.2.38 K a,2 H + 1.2.34C 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 1.2.39 27
InH pk a ph ph ph pk a 1.2.5.6. ph ph 7 ph 4 ph 1.2.4.2. 1.2.1.3. ph 1-2-10 ph ph 0.10.3 ph V ph 1-2-10 1.2.6. 28
1.2.6.1. λ = 200400 nmλ = 400800 nm πnd I C M 1-2-11 λ 1.2.40 1-2-11 1.2.41 ελ M 1 cm 1 λaλ tλ Tλ 1.2.42 1.2.411.2.42 1.2.43 -Lambert-Beer Aλ C Aλλ 1-2-12 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
π n p ε max 1-2-12 π π* n π*λ max σ π d* d σ*π* d d d ε max = 0.1 1-2-12 0.02mM = 1 cm ε max > 1-2-4 1-2-4 λ(nm) 400 430 430 480 480 490 490 500 500 560 560 580 580 595 595 610 610 750 750 800 1.2.6.2. log t C t F 1.2.44 1.2.421.2.43dCC 1.2.45 30
F 1.2.46 F A 1-2-13 F A = 0.434 A = 0.20.8 A 1.2.6.3. 1-2-14 t t = 0 t = 1 1-2-14 W D 2 λ > 350 nm λ < 360 nm 31 1-2-15
1-2-15 NO 3 200 nm 1.3. 1.3.1. Excel p.45 1.3.1.1. TARE 0.0000 g 10 ml 32
W g 9 W 2 W 10 W W 0 90P = 0.10Dixon Dixon W W 0 n 10( )(s) c 1.2.2.4 10 ml V ml 95%F 95% V 10.0 ml 1.3.1.2. 1000 µl 200 µl 20 µl P-1000P-200P-20 1000 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
CV 1-3-1 1.2.2.4. V ml% = 100V V o V o ; V o 1-3-1 CV O- 1-3-1 µl CV P-20 20 1.0 0.30 P-200 200 0.8 0.15 P-1000 1000 0.8 0.15 1.3.2. ph ph ph CLR + CAL ph F + CAL H 3 PO 4 ; Mw 98.00 0.1 M f B 3L ph ph 4 MR 0.1 g 45 ml 50 ml25 PP 0.5 g 45 ml 50 ml25 34
!! 1.2 g 100 ml Fill-up P.10 100 ml 10 ml 40 ml 1 2 0.1 M NaOH 11015 0.1 M NaOH ml W mg 0.1 M NaOH f B H 3 PO 4 NaOH 0.1 M NaOH 1 ml = 9.800 mg H 3 PO 4 1.3.7 W wmg Pww%1.2.3.3. 1-2-2 ph 1.2.30 pk a,2 H 2 PO 4 pk a ph 1.2.31 pk a,1 H 3 PO 4 pk a 1.2.31 C A W (40 ml) ph 1.2.32 pk a,3 HPO 4 2 pk a 1.2.32 C A ΔpH ΔV B ΔV B ΔpH ph 1.2.20β ΔC B ΔpH ΔC B = C B f B ΔV B V t β V t ml 35
β C B f B ΔV B ΔpHV t ph ph ph pk a Excel ph 1.3.3. 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 1.3.17 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 = 10.26 1.3.18 1-3-1 α H ph K MY,app ph ph 36 1-3-2 EBT
Mg 2+ EDTA logk MY 8.69 ph10 ph 11 Mg(OH) 2 Mg 2+ ph 1011 EBT Ca 2+ logk MY 10.59 ph 13 ph 813 1-2--4--1--2--3- NNMg 2+ Ca 2+ Mg 2+ Mg 2+ Ca 2+ ph 1213 Mg 2+ Ca 2+ EDTA 1-3-2 ph 1.2.5.5. H + Ca 2+ 1-3-1 logα H ph Mg 2+ CaCO 3 Mw: 100.09 ppm ppm = parts per million = 10 6 0.01 M EDTA f E EDTA2Na2H 2 OMw 372.243.7224 g 1000.0 ml 6 Zn 25 6L 0.01 M f Mg MgCl 2 6H 2 OMw 203.301.0165 g 500.0 mledta 25 EBT 0.1% 1:1 50mL 14 g 114 ml 200 ml; 25 10 % 10 g + 100 ml25 10%NaOH 20 g + 200 ml25 NN1-2--4--1--2--3- K 2 SO 4 200 50.0 ml 0.01 M 1.00 mlph 10 1 mlebt 5,6 0.01 M EDTA V E,t ml Mg 2+ EBT MgCl 2 37
2 50.0 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 3 0.01 M EDTA 1mL = 1.0009 mg CaCO 3 ppm= 1.0009f E V E,t 1.00f Mg 100050 1.3.19 V E,Ca ml 0.01 M EDTA f E ppm = 1.0009f E V E,Ca 100050 1.3.20 EDTA Mg 2+ Ca 2+ logk MY 1-3-1 α H ph ph logk MY,app 8 1.3.17K MY,app 1.3.4. C C L-ascorbic acid, AsAdehydroascorbate; DAsA AsA 2,6-2,6-dichlorophenolindophenol; DCIP 38
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 3 5 5 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 3 1.3.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
5% HPO 3 ; Mw 79.98 37%150g 2.85 L 25 2% 5% 40 ml 60 ml AsA 4mg100mL; 0.2 mm AsAC 6 H 8 O 6 ; Mw 176.1320 mg 2% 500 ml 100 ml AsA 6% KI KIMw 166.00 6 g 100 ml 25 5 mm KIO 3 KIO 3 Mw 214.001 0.5 g214 0.005 0.5 = 0.535 W g 500 ml 5 mm KIO 3 W 25 f (KIO 3 ) = W214.0010.0050.5 0.2 mm KIO 3 5 mm KIO 3 20 ml 500 L 0.5% 0.5 g 100 ml 25 0.5 mm DCIP DCIP-Na2H 2 OC 12 H 6 Cl 2 NNaO 2 2H 2 O Mw 326.110.45 g 3 L 25 100 ml AsA 20 ml 6% KI 1 ml 34 0.2 mm KIO 3 VKIO 3 mlasa AsA C mgmlf KIO 3 0.2 mm KIO 3 1 ml = 3 0.2 176.131000 = 0.1057 mg AsA 1.3.A8 C mgml = 0.1057fKIO 3 VKIO 3 20.0 1.3.A9 100 ml AsA 20 ml DCIP (DCIP 1mL AsA A [mgml]dcip V(DCIP) [ml] AmgmL = 20.0CVDCIP 1.3.A10 40
5% 2 2.0 ml 5% 7.0 ml 8.0 ml d = 217 100 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 1.3.5. 1.3.24 sucrose glucose fructose (H 2 O 2 ) 41
1.3.25 glucose gluconic acid H 2 O 2 3,3,5,5 -(TMB) 1.3.26 TMB π π* 0.20 mgml C 12 H 22 O 11 : Mw = 342.30 0.1 g 500 ml 25 5 ml 0.1 mgml C 6 H 12 O 6 Mw = 180.16 0.1 g 1000 ml 25 5 ml 0.1M ph6.0 0.1 M ph6.0 1000 ml 25 150 mg2000 U100 ml 0.1 M ph6.0 25 23 ml 45 mg 9 ml 0.1M ph6.0 25 TMB TMB2HClMw 313.26 45 mg 9 ml 25 GPO 36 mg 90 ml 0.1M ph6.0 9 mltmb 9 ml 0.1M ph6.0 900 ml 25 42
20 ml 1 M H 2 SO 4 190 ml H 2 SO 4 11 = 200 ml 1 M18 M)25 3 ml 0.1 mgml 0.2 mgml P-20 1.3.8 37 30 O 1.3.8 202515 1 M H 2 SO 4 0.1 ml 450 nm A r r > 0.995 p.46 mg100 ml 1.3.8 µ 43
glc suc O H 2 SO 4 0 0 0 0 2300 1000 100 20 0 0 0 2280 1000 100 40 0 0 0 2260 1000 100 60 0 0 0 2240 1000 100 80 0 0 0 2220 1000 100 100 0 0 0 2200 1000 100 0 40 0 200 2060 1000 100 0 80 0 200 2020 1000 100 0 0 20 200 2080 1000 100 0 0 20 0 2280 1000 100 0 0 40 200 2060 1000 100 0 0 40 0 2260 1000 100 0 0 100 200 2000 1000 100 0 0 100 0 2200 1000 100 44
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
R R r Memo 46