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ph ph

2013 by Mettler-Toledo AG CH-8902 Urdorf/Switzerland

10 1 ph 11 1.1 11 1.2 ph 13 1.3 ph 14 1.3.1 ph 15 1.3.2 17 1.3.3 18 1.4 ph 19 2 20 2.1 ph 20 2.2 ph 21 2.2.1 ph 21 2.2.2 ph 23 2.2.3 26 2.2.4 30 2.2.5 31 2.3 32 2.3.1 32 2.3.2 35 2.3.3 35 2.4 39 2.4.1 39 3 44 3.1 44 3.2 45 3.3 45 3.4 47 3.4.1 47 3.4.2 48 ph - 5

4 49 4.1 49 4.1.1 49 4.1.2 PTFE 51 4.1.3 52 4.1.4 52 4.2 53 4.3 57 4.4 ph 58 4.4.1 58 4.4.2 59 4.4.3 60 4.4.4 61 4.4.5 ph 61 4.4.6 ph 62 4.4.7 ph 63 4.4.8 63 4.4.9 (ISFET) ph 64 4.4.10 64 4.5 65 4.6 65 4.6.1 66 4.6.2 66 4.7 66 4.7.1 (Ag 2 S) 66 4.7.2 (AgCl) 66 4.7.3 67 4.7.4 67 4.8 67 6 ph -

5 ph 68 5.1 ph 68 5.2 69 5.3 72 5.3.1 (ß 74 5.3.2 ( ph) 75 5.3.3 ( ph / T) 75 5.4 ph 75 5.4.1 ph 77 5.4.2 78 5.5 / ph 81 5.6 ph 82 5.6.1 82 5.6.2 82 5.6.3 83 5.6.4 84 5.7 85 5.7.1 85 5.7.2 86 5.7.3 86 5.7.4 87 5.8 89 6 95 ph - 7

1 11 2 11 3 ph 11 4 ph 12 5 12 6 ph 14 7 ph 15 8 16 9 ph ph 16 10 17 11 ph ph 18 12 ph 19 13 InTrac 776 e 24 14 25 15 26 16 29 17 ph 34 18 37 19 Equithal 38 20 40 21 50 22 PTFE 51 23 52 24 ph 53 25 ARGENTHAL 54 26 ph 57 27 InPro 200x (i) 59 28 InPro 426x (i) 59 29 ph 60 30 InPro 480x (i) 61 31 InPro 325x (i) 62 32 InPro 4850 i 62 33 phure Sensor 63 34 InPro 3100 (i) 63 8 ph -

35 InPro 3300ISFET ph 64 36 InPro 4501 64 37 InPro 4550 65 38 74 39 ph 76 40 76 41 79 42 ph ph ph 81 43 83 44 86 45 ph 87 46 89 47 / 90 ph - 9

ph ph ph ph ph ph ph Urdorf2013 1 10 ph -

1 ph 1.1 (H 3 O + ) (OH ) ph H 3 O + + OH 2 H 2 O 1 CH 3 COOH + H 2 O CH 3 COO + H 3 O + 2 ph 5.2 69 ph = log [a H +] 3 ph ph - 11

ph ph 4 ph / 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 4.9 % (1M) 0.37 % (0.1M) 0.6 % (0.1M) 4% 0.27 % (0.1M) 1.7 % (1M) 0.017 % (0.01M) 0.98 % (0.1M) 0.84 % (0.1M) 4 ph ph 7 14 OH ph NH 3 + H 2 O NH 4+ + OH 5 ph ph 0 14 0 7 ph 7 14 ph ph 7 12 ph -

1.2 ph ph ph ph ph ph ph ph ph ph ph ph ph ph - 13

ph 1.3 ph ph ph ph ph ph ph H + / H + ph ph 6 E = E 0 + 2.3 RT log [a H +] nf 6 ph E = R = n = E 0 = T = F = 14 ph -

ph 7 ph 7 ph ph ph ph 1.3.1 ph ph ph H + 8 ph - 15

ph H + = SiO 3 Li + SiO 3 Li + SiO Li + 3 Li + SiO 3 SiO Li + Li + 3 SiO 3 Li + SiO SiO 3 3 SiO 3 SiO 3 Li + SiO Li+ 3 H + H + H + H + (0.2 0.5 mm) 1000 A (10-4 mm) 8 H + ph H + H + H + ph ph ph 9 9 ph ph 16 ph -

1.3.2 ph H + ph 10 10 / / 5.4 ph 75 ph - 17

ph 1.3.3 11 ph ph ph ph ph 11 ph ph 18 ph -

1.4 ph ph ph ph ph ph ph ph 12 ph ph - 19

ph 2 2.1 ph ph ph ph ph ph ph 20 ph -

2.2 ph 2.2.1 ph ph ph ph 5.6 ph 82 ph ph ph ph ph - 21

ph ph 479.2 5 0.01 ph p H ph 2.4 39 ph ph 0.02 ph 2.3 32 22 ph -

2.2.2 ph ph 14 25 ph ph ph ph 15 ph ph ph ph ph ph ph ph ph - 23

ph ph 13 ph 13 InTrac 776 e 24 ph -

PVDF 1 2 1 / 2 3 4 5 6 3 4 5 14 ph - 25

ph 2.2.3 ph ph 15 ph ph 5.6 ph 82 E ph t ph 15 26 ph -

2.2.4 30 ph ph ph ph ph ph 2.2.3 26 10 C 0.15 phph 3 11 5.6 ph 82 ph ph ph IP65 ph ph - 27

ph 10 20 28 ph -

PLC 16 ph - (ISM) 3 44 ph - 29

ph 2.2.4 ph 0 mv ph ph 7 5.5 / ph 81 0 mv ph 7 ph ph 2 ph ph ph 7 ph ph 30 ph -

2.2.5 (NIST) ph DIN 19266 0.02 ph ph ph - 31

ph 2.3 ph 2.3.1 80 C / 17 34 32 ph -

/HCl /HCl 0.1 mol / L NaOH 0.1 mol / L HCI 15 ph - 33

ph 17 ph 34 ph -

2.3.2 2.3.3 ph (0-14) H + OH [H + ] [OH ] = 10 14 = I (25 C) ph ph - 35

ph ph ph / H + ph / 20 C 30 C 0.001 mol / L HCI ph 3.00 ph 3.00 0.001 mol / L NaOH ph 11.17 ph 10.83 ph 7.43 ph 7.40 ph 7.84 ph 7.56 ph ph E = E 0 2.303 RT / F phr,f = E = E 0 = ph = ph F = R = T = 5.6 ph 82 36 ph -

} (ph 7 = O mv) 18 +mv E is ph 0 7 14 T 1 mv T 2 T 2 >T 1 18 ph ph = 7 0 mv/ 25 C ph 7 0.1 ph 5.6 ph 82 ph - 37

ph / ph 0.5 80 C 30 C ph Equithal 0 10 20 30 t Equithal Equithal 19 Equithal ph 7 0 mv 19 38 38 ph -

2.4 40 2.4.1 2.2.4 30 5.5 / ph 81 2.2.4 30 5.3 72 ph - 39

Y 1 2 2 Y N 1 N Y N Y 3 N 12 Y N 4 Y Y N 6 7 Y 20 40 ph -

41 ph - 8 9 10 11 1 1 5 Y Y Y Y Y Y Y Y N N* N N N N N N 1 * N N N Y N >30 mv

ph <<>> 1 ph 85 % 102 % ± 30 mvdin 2.2.4 30 5.5 / ph 81 2 ph 2.3.3 35 5.3 72 3 4 2.3.1 32 42 ph -

5 2.2.3 26 6 2.3.3 35 5.6 ph 82 7 8 85% 9 102% 10 ± 30 mv (± 0.5 ph; 25 C) DIN ± 30 mv 11 12 ph - 43

ph 3 ph - (ISM) ISM ISM ISM 3.1 ph mv ph ISM ph ph ph ph / PLC ISM ISM 44 ph -

3.2 ISM isense Asset Suite ISM 3.3 ISM ISM PLC ph - 45

ph DLI Dynamic Lifetime Indicator ACT Adaptive Calibration Timer DLI ph ACT DLI TTM Time to Maintenance 00/NN CIP CIP/SIP Counter CIP/SIP CIP SIP CAL Calibration History Max. C Days of operation MAX Max. Temperature/ODI / 46 ph -

3.4 isense Asset Suite ISM isense ISM isense PC isense ISM ph ph isense ISM 3.4.1 PC isense CIP / SIP isense PDF ph ph - 47

ph 3.4.2 ISM ph isense CIP/SIP isense (DLI)DLI - ph DLI ISM DLI isense SQL ISM 48 ph -

4 ph ph ph ph ph 4.1 4.1.1 ph - InPro 325x 21 ph - 49

ph 21 KCl AgCl KCl Ag 2 S / ph 50 ph -

4.1.2 PTFE PTFE PTFE ph PTFE - InPro 480x PTFE ph 22 PTFE ph - 51

ph 4.1.3 Xerolyt EXTRA 23 4.1.4 ph ph 52 ph -

ph- 24 ph - InPro 4850 i ph ph ph ph ph (pna) pna ph ph ph pna 4.2 /// / ph - 53

ph / AgCl Ag / AgCl AgCl AgCl ARGENTHAL ARGENTHAL AgCl AgCl AgCl Ag/AgCl (ARGENTHAL ) Ag + 25 ARGENTHAL ARGENTHAL ph KCl LiCl 54 ph -

Ag / AgCl AgCl 25 54 AgCl AgCl 3 mol / L KCl ARGENTHAL AgCl AgCl ARGENTHAL ARGENTHAL 3 mol / L KCl AgCl 3 mol / L KCl Ag+ ph - 55

ph / ARGENTHAL ARGENTHAL 3 mol / L KCl + H 2 O 3 mol / L KCl + AgCl + H 2 O LiCl + / LiCl + 56 ph -

4.3 ph 26 ph ph 26 ph - ph ph - 57

ph HA: LoT: A41 HF: Na: - / ph 1g / L ph HF (> 1g / L) ph 5 ph 4.4 ph ph ph 4.4.1 ph ph InPro 200x (i) 58 ph -

27 InPro 200x (i) 4.4.2 ph ph ph Xerolyt Extra- InPro 426x 28 InPro 426x (i) ph - 59

ph 4.4.3 ph - ph ph 29 ph 60 ph -

4.4.4 ph / (PTFE) - InPro 480x (SG) 30 InPro 480x (i) 4.4.5 ph - InPro 325x (i) ph InPro 325x ph ph - 61

ph 31 InPro 325x (i) 4.4.6 ph ph ph - InPro 4850 i ph ph ph 32 InPro 4850 i 62 ph -

4.4.7 ph / /- Thornton phure Sensor 33 phure Sensor 4.4.8 - InPro 3100 UD 34 InPro 3100 (i) ph - 63

ph 4.4.9 (ISFET) ph ISFET ph - InPro 3300 ph (ISFET) 130 C 6 bar (PED 97) 45 ph 35 InPro 3300ISFET ph 4.4.10 - InPro 4501/ 4550 PVDF PPS NPT 36 InPro 4501 64 ph -

37 InPro 4550 4.5 ph 4.6 ph ph ph ph ph - 65

ph 4.6.1 3 mol / L KCl ph 4 ph 7 4.6.2 ph 4 0.1 mol / L HCl ph 4.7 ph 4.7.1 (Ag 2 S) 8 % 0.1 mol / L HCl 4.7.2 (AgCl) AgCl 66 ph -

4.7.3 /HCI 5 % 0.1 mol/l HCl 4.7.4 0.1 mol / L HCl 4.8 ph 1 2 ph ph ph ph - 67

ph 5 ph ph ph ph ph 5.1 ph Sorenson ph H 3 O + ph = log [a H +] H 3 O + ph ph ph H+ ph IUPAC oxonium (H 3 O + ) H + + H 2 O H 3 O + 2 H 2 O H 3 O + + OH 68 ph -

Kw Kw = [H 3O + ] [OH ] = [H3 O + ] [OH ] = 10 14 (25 ºC) [H 2 O] K w H 3 O + OH [H 3 O + ] [OH ] 10 7 mol / LpH 7 H 3 O + ph ph 10 3 mol / L H 3 O + [OH ] = 10 11 mol / L ph 3 ph 5.2 ph ph (a H+ ) (γ H+ ) b = mol / kg c = mol / L a H+ = γ H+ b H+ a H+ = b H+ ph - 69

ph (T) (I) (z) (d) ph γ x H+ log γ x H+ = 0.5 I½ 1 + 3 I ½ I = ½ c i z i 2 ph z i 1 0.001 0.005 0.01 0.05 0.1 0.967294 0.935044 0.915247 0.857205 0.829586 70 ph -

0.01 mol / L HCl ph 0.01 mol / L HCl 0.09 mol / L KCl 0.01 mol / L HCl ph = log (b H+ γxh + ) = log (0.01 0.915) = log (9.15 10 3 ) = 2.04 ph = log (b H+ γxh + ) = log (0.01 0.829) = log (0.829 10 3 ) = 2.08 ph 0.04 ph H + ph γ m H+ H + H + 200 a H+ = γ x H+ γ m H+ b H+ ph ph - 71

ph 5.3 ph ph ph ph ph HA H + + A A HA (A ) HA H + A H + HA A ph 72 ph -

Ka = [H+ ] [A ] [HA] 1 = 1 [A ] [H + ] K a [HA] log 1 1 = log + log [A ] [H + ] K a [HA] log 1 = log [H + ] = ph [H + ] log 1 = log K a = pk a K a ph = pk a + log [A ] [HA] - [A ] = [HA] ph ph = pk a pka ph - 73

ph 5.3.1 (ß ph ph = pka ph = pka 1 (CH 3 COOH) ( 38) OH pk a 4.8 ph ph ph ph=pk a [A ]=[HA] ph 4.8 ph ph 4.8 [A ]/[HA] 38 / CO 2 74 ph -

5.3.2 ( ph) ph ph ph 5.3.3 ( ph / T) ph H + ph ph 5.4 ph 1.3 ph 14 ph ph 7 15 ph E E E = E 0 + 2.3 RT log a H+ nf 6 14 ph - 75

ph (SHE) (NHE) SHE SHE ah + = 1.0 1 bar E 0 ah+ = 1 2.3 RT / nf (EN) ph H + ph EN T 39 E N (mv) / ph 0 C E N = 54.2 mv / ph 25 C E N = 59.2 mv / ph 50 C E N = 64.1 mv / ph 39 ph E 40 E E 4 E 3 E 2 E5 E 6 E 1 40 76 ph -

5.4.1 ph ph E1 ph E1 ph E2-E6 ph E6 ph ph E2E3E4 E5 40 76 ph E1 ph 8 16 ph ph ph 40 76 E2 H + Li + ph 40 76 E3 ph E3 ph (E4) ph - 77

ph 5.4.2 ph (E1-E4) ph (E5-E6) E5 / / E6 (E6 / E diff ) E diff ph E diff 78 ph -

H + OH 41 25 C 10 4 cm 2 / s V H + 36.25 OH 20.64 Li + 4.01 F 5.74 Na + 5.19 Cl 7.91 K + 7.62 NO 2 3 7.41 NH 4 + 7.62 CH 3 COO 4.24 1 Na + CI 2 + 41 ph - 79

ph 1 2 Cl Na + E diff ph E diff ph KCI KNO 3 41 79 ph 25 C ph KCl HCl (1 mol / L) E diff = + 14.1 mv 0.238 ph KCl NaOH (1 mol / L) E diff = 8.6 mv 0.145 ph 80 ph -

ph 5.5 / ph ph (mv) (mv / ph) ph 7.00 ph ph 4.01 9.21 10.00 0 mvph 7.00 mv 59.16 mv / ph25 C = 59.16 mv/ph 9 mv 7 ph 7 ph = 57.8 mv/ph mv mv 42 ph ph ph ph - 81

ph 5.6 ph 5.6.1 ph ph mv ph E = E 0 + 2.3 RT log a H+ nf, (T) E = E 0 0.198 T ph ph 5.6.2 E1 E6 (ph 7.00 / 0 mv) ph E1 E6 ph 7 0.1 ph ph 43 82 ph -

mv 7 14 ph T 1 } T 2 43 5.6.3 ph ph ph ph - 83

ph 5.6.4 ph ph ph 0 C 100 C 1.34 ph Kw (γ) γ 1 γ pk s H + ph / 84 ph -

ph 20 C 30 C 0.001 mol / L HCl 3.00 3.00 0.001 mol / L NaOH 11.17 10.83 7.43 7.40 7.84 7.56 ph ph 5.7 5.7.1 ph H + ph H + H + ph - 85

ph ph (ph > 9) ph 44 5.7.2 H + ph ph 44 mv 0 14 ph 44 5.7.3 KCl Hg 2 +, Ag +, Pb 2 +, CIO 4 86 ph -

(E diff ) ph 5.7.4 5% ph ph ph ph 0 ph 14 ph H + ph 45 87 ph 0 7 14 21 28 ph 45 ph ph - 87

ph ph ph ph ph ph ph ph 88 ph -

5.8 46 ph ph ph 4 7 ph - 89

ph ph 4 20 ma 4 ma 47 / ph 1 2 1 90 ph -

ph ph 2 3 ph 3 3 2 IP65 10 C + 50 C IEC 0.005 ph ph - 91

ph de/dt < 25 10 6 V / C R in > 10 12 Ohm < 10 12 A l b R in = 10 12 Ohm l b = 0.5 10 12 A (25 C); l b 2.8 10 12 A (50 C) de/dt = 20 10 6 V / C RM = 500 10 6 Ohm 92 ph -

R M E in Rin E G E in = R in E G R M + R in ~ R M (phi ph a ) R in > R M R in ph R M : E G : ph a = 4 0.002 ph R in 10 12 Ohm ph - 93

ph 25 C 50 C E in = R M I b R M I b E in = 1.15 mv = 0.018 ph E = de T T = 25 C dt E = 500 10 6 V = 0.008 ph = 0.033 ph 94 ph -

6 a = b = mol / kg ß = c = γ = F = (96485 A s mol 1 ) I = pha = ph pk = ph R = (8.3143 Nm K 1 mol 1 ) S = mv/ph T = (K) E diff = E el = E 0 = E N = v = z = ph - 95

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