I II 2009
1. 2. 12 50 3. 1. 2. 3 ( 0.1g, 0.01g, 0.001g ) 3. 4. 1. 2. ()A4 3.
000005 19 5 11 () 19 5 15 () EDTA " # $ 1000 500 =... mol/l
Web 1) p.159 2) 1987pp.14-15 3) 1989pp.58-60 4) http://www.chem.zenkyo.h.kyoto-u.ac.jp/operation/
A S E S
1/2 1) 2) 1 (100ml 10ml)50mL 500ml () A. 60mg70mg (100ml) (Fig.1) Fig.1
(Fig.2) Mg (mg) H2 (ml)() (mmhg)( 1) Fig.2 B. 5060mg 20 (Fig.3) (100ml) 500ml (Fig.4) (Fig.4) Fig.3 Fig.4 Fig.5
( ) 70 (Fig.5) Fig.6 (10ml)(Fig.6) Al (mg)(ml)()(mmhg)( 2) A. ()()( 3) ) ()() (P)(V)(T) 2) (n) 1/2 (m[g]) z n 1:1/2z:n m[g] z=2n x[g/mol] 1:xz:m xm/2n B. A A
Mg Al Mg Al 30.0 60.0% 1.0010 5 N/m 2 1.00m 3 0% 78% 22% :28.0:32.0:18.0 26.98 pvnrt 24.31 p:(atm) 1atm=760mmHgV:(L)T:(K) K=+273 R: 0.08206 (atm L K 1 mol 1) p:(nm 2) 1atm=1.01310 5 Nm 2V:(m 3 ) 1m 3 =10 3 L T:(K)R: 8.314 (JK 1 mol 1) () -15-14 -13-12 -11-10 -9-8 -7-6 -5-4 -3-2 -1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 mmhg 1.436 1.560 1.691 1.834 1.987 2.149 2.326 2.514 2.715 2.931 3.163 3.410 3.673 3.956 4.258 4.579 4.926 5.294 5.685 6.101 6.543 7.103 7.513 8.054 8.609 9.209 9.844 10.518 11.231 11.987 () 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 mmhg 12.788 13.634 14.530 15.477 16.477 17.535 18.650 19.827 21.068 22.377 23.756 25.209 26.739 28.349 30.043 31.824 33.695 35.663 37.729 38.898 42.175 44.563 47.067 49.692 52.442 55.324 58.34 61.50 64.80 68.26 () 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 mmhg 71.88 75.65 79.60 83.71 88.02 92.51 97.20 102.09 107.20 112.51 118.04 123.80 129.82 136.08 142.60 149.38 156.43 163.77 171.38 179.31 187.54 196.09 204.17 214.17 223.73 233.7 243.9 254.6 265.7 277.2 () 75 76 77 78 79 80 81 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 mmhg 289.1 301.4 314.1 327.3 341.0 355.1 369.7 384.9 400.6 416.8 433.6 450.9 468.7 487.1 505.1 525.76 546.05 566.99 588.60 610.90 633.90 657.62 682.07 707.27 733.24 760.00 787.57
NaOH Na2CO3 NaOH Na2CO3 NaOH + HCl NaCl + H2O Na2CO3 + HCl NaHCO3 + NaCl NaHCO3 + HCl NaCl + H2CO3 (1a) (1b) (2) Fig.1 ph (1a) (1b)(2) ml NaHCO3 Na2CO3 Na2CO3 ml HCl Na2CO3 NaOH Fig.1 Na2CO3 NaOH BaCO3 NaOH NaOH (1)(CO3 2 OH ) NaOH + HCl NaCl + H2O Na2CO3 + 2HCl 2NaCl + H2O + CO2 (3a) (3b) (2) NaOH Na2CO3 + BaCl2 BaCO3 + 2NaCl (4) NaOH + HCl NaCl + H2O (5)
200mL 500mL 15mL 10mL 100mL 150mL (NaOHNa2CO3) A. 0.1M HCl 15mL 50100mL 0.1M 0.0 () (Fig.2) (Table 1) 1 0.1M HCl 0.03mL 3 Fig.2 (25mL) B. (1) 15mL 50100mL 1 0.1M HCl 0.03mL (2)NaOH 15mL 50100mL 10%BaCl2 5mL 10%BaCl2
HCl 0.03mL NaOH Na2CO3 (mol/l)(g/l) 100mL 0.01M NaOH 10mL 0.01M 4.3mL C[mol/L] HA Ka ph C[mol/L](Na2CO3) Kb1Kb2 ph NaOH 40.00 Na2CO3 105.99 BaCl2H2O 244.26
ph HA H + A HA C a C a = [HA] + [A ] (), [H ] = [A ] + [OH ] [A ] = [H ] [OH ], [HA] = C a [A ] K a H + A - H + ( H + OH - ) K a = K a = HA C a ( H + OH - ) [H ] >> [OH ](1) [H ] 2 + K a [H ] K a C a = 0 [H ] C a CH 3 COONa Na + + CH 3 COO () CH 3 COO + H 2 O CH 3 COOH + OH CH 3 COO CH 3 COOH CH 3 COO CH K b = 3 COOH OH - CH 3 COO - (2) CH 3 COOH H + CH K a = 3 COO - CH 3 COOH (3) (2),(3) K a K b = [H ] [OH ] = K w buffer solution H [H + ] () -: CH 3 COOH CH 3 COO C a mol CH 3 COOH C b mol CH 3 COONa 1 L (1 dm 3 ) () [CH 3 COOH] + [ CH 3 COO ] = C a + C b, [Na ]= C b () [H ] + [ Na ] = [ CH 3 COO ] + [OH ] [CH 3 COOH] [ CH 3 COO ](3) H + ( C K a = b + H + OH - ) C a ( H + OH - ) C a, C b >> [H + ] [OH ] [H + ] = K a C a /C b ph = pk a log 10 (C a /C b )ph = pk a log 10 ( [] / [])
b = dc a / d(ph) C a, C b >> [H ] - [OH ] b = 2.3 C a C b / (C a +C b ) b 0.1 mol/l 0.1 mol/l 0.1 mol/l ph 25K a =1.810-5 ph (Horiba ) [ Horiba ph ] (1) (2) ph (3) 1 1 ph Navi ph D-51 (1) ON/OFF CAL CAL (2) (3) (4) ph 7 3 (5) CAL HOLD (6) HOLD ph (8) (9) ph 4 ph 9 (10) (11) 3 ph (12) MEAS HOLD (13) HOLD (14)
(15) ON/OFF 1 ph 4 --- ( 10.21 g 1 L ) 20 : ph = 4.00, 25 : ph = 4.01, 30 : ph = 4.02 2 ph 7 --- ( 3.40 g 3.55 g 1L ) 20 : ph = 6.88, 25 : ph = 6.86, 30 : ph = 6.85 3 ph 9 --- ( 3.81 g 1 L ) 20 : ph = 9.22, 25 : ph = 9.18, 30 : ph = 9.14 4 ph 4 ph 9 ph (1) 0.1 mol/l 1 60.05 991.049g /cm 3 3 ml 500 ml 500 ml (2) 0.2 mol/l NaOH 20 ml 2 mol/l NaOH 200 ml 200 ml (3) 0.2 mol/l HCl 1 10 ml 2 mol/l HCl 100 ml 100 ml (4) 0.1 mol/l 1 CH 3 COONa3H 2 O 136.09 98.5 CH 3 COONa3H 2 O 136.09 3.4 250 ml 250 ml (1) 0.1 mol/l 50 ml 100 ml ph (2)20 ml 0.1 mol/l 20 ml 100 ml ph 2 0.1 mol/l 128 1 ph ph 0.1 mol/l 2 4 8 16 32 64 128
(1) 0.1 mol/l 0.1 mol/l 50 ml 200 ml (2) 0.1 mol/l 30 ml 100 ml 50 ml ph (3) 10 ml 1 0.1 mol/ 10 ml 100 ml 100 ml 10 (4) 3 10 20 ml ph 100 1000 ph ph 0.1M 10 100 1000 ph (1) 50 ml 100 ml ph (2) (1)1 ml 0.2 mol/l 1 ml ph 1 ml 0.2 M 1 ml 4 ml ph ph 1 50 ml 2 1 0.2 mol/l NaOH 1mL 3 2 0.2 mol/l HCl 1mL 4 3 0.2 mol/l HCl 1mL 5 4 0.2 mol/l HCl 1mL 6 5 0.2 mol/l HCl 1mL
(1) 50 ml 100 ml ph (2) (1)1 ml 0.2 mol/l 1 ml ph (3) 1 ml 0.2 mol/l 1 ml 4 ml ph (4) ph 1 0.1 mol/l 50 ml 2 1 0.2 mol/l NaOH 1mL 3 2 0.2 mol/l HCl 1mL 4 3 0.2 mol/l HCl 1mL 5 4 0.2 mol/l HCl 1mL 6 5 0.2 mol/l HCl 1mL mol/l () ph a b 4 c ph ()
C A HA C B BOH a = C B /C A [H ] A [H ]=[H] C B = 1 # K w % C A C A $ [H] "[H] & 1 ( + (A) ' 1+[H]/K a C B = [B], C A = [A] + [HA] [B] + [H] = [OH] + [A] C B = [OH] [H] + [A] = K W /[H] [H] + [A] ---- (1) K a [HA] = [A][H] / K a (1) C A C B = 1 # K w % C A C A $ [H] "[H] & [A] ( + (A) ' [A]+[A][H]/K a ph 2 C B = 1 # K w % C A C A $ [H] "[H] & 2+[H]/K ( + a 2 ' 1+[H]/K a 2 +[H] 2 /K a 2 K (B) a1 H 2 A C A BOH C B C B = [B], C A = [A] + [HA] + [H 2 A] (2) [H] + [B] = [OH] + 2[A] + [HA] (3) (2)(3) [H] + C B = K W /[H] + 2C A [HA] 2 [H 2 A] C A C B /C A = ( K W /[H] [H] ) / C A + 2 ( [HA] + 2 [H 2 A] ) / C A [HA]=[A][H]/K a2, [H 2 A]=[A][H] 2 /K a1 K a2, C A = [A] ( 1 + [H]/K a2 + [H] 2 / K a1 K a2 ) C B = 1 # K w % C A C A $ [H] "[H] & ( + 2 [H]/K + a 2 2[H]2 /K a 2 K a1 (B)' ' 1+[H]/K a 2 +[H] 2 /K a 2 K a1 +2 (B) (B)' 1 + [H]/K an + [H] 2 / K an K an-1 + ------+[H] n / K an K an-1 K a1 [H]/ K an + 2[H] 2 / K an K an-1 + ------+ n [H] n / K an K an-1 K a1 (B)' 2 n (B)' A (A H )= C A /[A] (B)' A 1987
pk a = 4.58 pk a1 = 1.84, pk a2 = 5.83 NaOH (A)(B)[H + ] C B /C A 0.1 mol/l ph SK-620pHRS232C ph SK-620PH (1) OFF OFF 20 PWR CAL PWR ncal (2) (3) CAL [4.00]CA: (4) ph 4 (5) ph/mv () () ph 4.01 25 ph 4.01 ph 7pH
(6) REC SA ph 4 (7) ph7 (8) ph 4 ph 7 ph 10 (9) 3 ph 10 End ph (10) ph ph (11) PWR OFF 1CA 4 XXX.XmV 2SK-620PH ph ( ph 1.68 at 25 ) ( ph 9.18 at 25 ) ph4 ph7 ph10 3.50 4.50 6.50 7.50 9.5010.50 3 ph 4 ph 7 7 ph 10 ( 20 : ph = 10.06, 25 : ph = 10.01, 30 : ph = 9.97 ) 1. ph SK-620PH PC ( RS-232C ) 2. XL232Logger.xls XL232Logger 3. [] 4. [] SK-620PH 5. SK-620PH F NaOH G H ph 6. [] ph 7. ph 0.01 m ph ph
XL232Logger.xls (RS-232C ) XL232Logger.xls SK-620PH
(1) 0.038 mol/l 1 HOOCCHCHCOOH 116.07 99.0 1.1250 ml 250 ml (2) 0.1 mol/l 0.2 mol/l NaOH 7. ph ph (3) ( ) 0.1012 g 100 ml ph 8.310.0 (4) ( ) 0.1 g 100 ml ph 3.14.4 1 (1) 20 ml 0.1 mol/l 300 ml 100 ml 80mL 100 ml (2) ph (0.02 mol/l ) (3) 1,2 0.2 M NaOH ph 1 ml ph -NaOH -ph (4) ph ph ph = 11 (5) 1 2 (1) 1 (2) 20 ml 0.038 mol/l 300 ml 100 ml 80 ml 100 ml ph 1, 2 0.2 M ph 11 (4) a b c
ph a ( = C B /C A ) d(ph) da " #(ph) #a da d(ph) " #a #(ph) Diff1 =(A6-A5)/(B6-B5) Diff2 =(B6-B5)/(A6-A5)
(EDTA) EDTA() 1) ( ) 2) () EDTA(H 4 Y) EDTA M n+ Y 4 MY n4 EDTA EDTA EDTA H 4 Y=H + +H 3 Y H 3 Y =H + +H 2 Y 2 H 2 Y 2 =H + +HY 3 HY 3 =H + +Y 4 ph Y 4 H + ph ph ph (H m In) (H m In) ph ph ph10 (BT) 3) ( H 3 In ) Mg 2+ ph HIn 2 Mg 2+ MgIn EDTA EDTA MgIn MgY 2 HIn 2 MgIn Y 4 MgY 2 HIn 2 OH 1) 100mL 500mL 500mL 50mL 15mL 25mL 300mL EDTA2NaNN BT
A. EDTA EDTA (1) EDTA EDTA2Na(EDTA H 4 Y Na 4 Y Na 2 H 2 Y ) 1.9g 500mL 500mL 2 0.5g 500mL ( ) 500mL 10mL 2.5mL 500mL 500mL ( ) (2) EDTA 15mL 300mL 50mL ph10 3) 2mL BT 4) 23 0mL EDTA 1 EDTA 0.03mL 3 EDTA B. ph 10 BT EDTA ph 10 50mL 300mL A(2) EDTA EDTA
C. ph 13 Mg(OH) 2 EDTA EDTA 50ml 300mL 8M KOH 2mL ph 13 35 NN EDTA ( ) (mol/l) (CaCO 3 )(g/g)(ppm 6) ) 7) ppm (a) (b) (c) ph ph 10 0.90 28wt% 1.8 10 5 ph MIn HY 3 MY 2 HIn 2
1) EDTA 2) EDTA (6 ) 3) 57mL 7g 100mL 4) BT ( 1-(-2-)-6--2--4- ) 0.5g 4.5g 100mL 6) (2) 1mol/L= 10 3 ppm 1[mol/L]100.09 10 3 1.0009 10 5 [ppm] (2) 7) 100.09
1,10-phenanthroline (II) Lambert-Beer c l I 0 I A = -log(i/i 0 ) = -log T = cl Lambert-Beer A T A c #$c! "! l %&'()*+
3 1. 500nm 2. ph 3. 0.01 mol/l Fe(II)Fe 2 4. (250, 100, 50ml) (II) ((NH 4 ) 2 SO 4 FeSO 4 6H 2 O)1,10- (NH 2 OHHCl) (CH 3 COOH) (CH 3 COONa) 1. (II)110-3 mol 100ml 0.0100 mol/l Fe(II) (II) N N!"#$%$&'()*+,-.+ 2. 0.0100 mol/l Fe(II)0.00100 mol/l Fe(II) 100ml 3. 1,10-1.2510-3 mol 250ml 0.00500 mol/l 1,10-(Phen)
4. 5% 50ml 5. 0.05 mol/l 250ml 6. 50ml 0.00100 mol/l Fe(II) 0.50, 1.00, 1.50, 2.50, 3.50, 5.00ml Fe(II) 2mlPhen 5ml 10ml Fe(II) 7. 400nm 8. Fe(II) 5.00 10-5 mol/l 410nm 10nm 500520nm 5nm 600nm 9. 100 10. 25ml 50ml 2mlPhen 5ml 10ml Fe(II) 11. 1g 300ml 6 mol/l 25ml 5ml 100ml 2ml 50ml 2mlPhen 5ml 10ml Fe(II) 1/10 0.0100 mol/l Fe(II)0.00500 mol/l Phen
500nm NH 2 OHHCl Lambert-Beer Fe(II)-Phen ( Aclc l 1cm c moll moldm -3, mol1000cm 3 1000cm 3 /mol ( 1000cm3(molcm )) A
0 10 M L MmLn. M a L b mm + nl!"#$ K = M m L n x (a-mx) m (b-nx) n
c x x A x dx/da=0 a/c m/(n+m) a/c a/c m/n 1. 2. 7 1. 7 1.0010-3 mol/l Fe(II) 1.0010-3 mol/l Phen 2. 25ml 10 1.0010-3 mol/l Fe(II) 2ml 3. NH 2 OHHCl 2ml 4. 1.0010-3 mol/l Phen 0, 1.00, 2.00, 3.00, 4.00, 5.00, 6.00, 8.00, 10.00, 12.00ml 5. 5ml 6. 7. 15 8. 100 9. 1. 1.0010-3 mol/l Fe(II) 1.0010-3 mol/l Phen 2. 25ml 11 1.0010-3 mol/l Fe(II) 3. NH 2 OHHCl 2ml 4. 1.0010-3 mol/l Phen 5. 5ml 6. 7. 15 8. 9.
Fe(II) Phen ml No. Fe(II) Phen Fe(II)!" Phen!" #$% &'" ()*+,!"-.()*+,!"/012!"3 1 0.00 10.0 2 0.50 9.50 3 1.00 9.00 4 1.50 8.50 5 2.00 8.00 6 2.50 7.50 7 3.00 7.00 8 4.00 6.00 9 6.00 4.00 10 8.00 2.00 11 10.0 0.00 1. Fe(II)-Phen 2. ph
(pcl)
(II) (1) (SO 3 H + ) CH 2 N + (CH 3 ) 2 OH (R H + )(M n+ ) CH CH 2 CH 2 CH CH 2 CH CH 2 CH CH 2 CH X CH CH CH 2 CH 2 CH 2 CH 2 CH CH 2!"#$%&'()*+,-../012345678 X M n+! + nr H K M H + [M = [M n+ n+ ][H ][H (R + + ] ]! n n ) n M n+ + nh + K M H H
1. H R H + Cu 2+ 2. 3. (II) 249.69, 105.99 (HCl)(II)(CuSO 4 5H 2 O)(Na 2 CO 3 ) 1. 3cm 1cm 2. 3mol/l HCl 100 ml 3. 4. 1.010-3 mol (II)(CuSO 4 5H 2 O) 25ml Cu(II) 5. Cu(II) Cu(II) 5ml 5ml
6. 0.05mol/l Na 2 CO 3 0.05mol/l Na 2 CO 3 500ml 7. (H + ) Cu(II) Cu(II) Cu(II) Cu(II)(H + ) Cu Cu 2+ III
1 Gibbs 0.0 1.0 0.0 1.0 0.0 1.0
0.0 1.0 2 3 a) b) c) - 1) - 2) 3) 30
4 1) - 2) 3) Sn-Pb -(1) (2) Sn (3) Sn Pb (4) Sn Pb -(1)(4) 4) Sn Pb Pb Sn 5 Pb-Sn
I II( ) MgAl MgAl MgAl MgAl mol
I II( ) NaOHNaCO3
I II 4 0.1mol/L 0.1mol/L 1 a 2 a 3 a 4 a a 3 4 b 4 ch
I II 5 0.1mol/L 1 a b c 0.038mol/L a 2 b c
I II( ) A EDTA EDTA B ph10 C ph13 D AD
I II 10 mol Cu 2+ H + Cu 2+ H + Cu Cu 2+ 1 2
[ Gibbs ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] [ ] 1889 pp. 14-23