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  • Acta Vol 53 p0001-0006

    Diunggah oleh

    Igor Vasiljevic
    6 tayangan6 halaman
    Chemistry journal 1999

    Judul Asli

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    Chemistry journal 1999

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    © All Rights Reserved
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    6 tayangan6 halaman

    Acta Vol 53 p0001-0006

    Diunggah oleh

    Igor Vasiljevic
    Chemistry journal 1999

    Hak Cipta:

    © All Rights Reserved
    Unduh sebagai PDF atau baca online dari Scribd
    Tandai sebagai konten tidak pantas
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    rie © hn Coie Soma 199 ‘iat tse Sot ete Cs Semin The Liquid Junction Potential in Potentiometric Titrations. 4. Determination of the lonic Molar Conductivities in Mixtures of Cd(ClO,)2+HCIO,+NaClO, under the Experimental Condition that /=3 M is Kept Constant Erzsébet Néher-Neumann “Department of Chemistry, Inorganic Chemistry, Royal Institute of Technology (KTH), S-100 44 Stockholm, Sweden pty NéterNeunann, E199. The Liquid aneton Polenta in Poenonei om Tita Deiertination of tie Tone Molar Contitvites in Mixture of Wo gy CA(CI0,), + HCIO, + NaClO, under the Experimental Condition that /=3 Mis ye" gg Kept Constant A&ta Chem, Scand 531-66 Acta Chemica Scandinavia 1999, @ N ‘The ionic molar conductivities have been determined in the tst solutions gor? some em cells containing mixtures of Cd(CIO,),-+ HCIO, + NaClO, unde experimental condition that (ionic sttength)=3 M is kept constant, Twas found thatthe ionic molar conductivities are either constant or linear function of the concentrations [H1"} or [Cd], respectively, The trace ionic molar onductvites of the CA" ions (8) and of the H™ ions (i) are diferent i the differnt mixtures studied, and they cannot be interchanged. Once the ionic molar conductvites had been oblained, the systemic eros preseat in the determined Ey values of the Nernst equations could be calculated. These errors aye: "O71 mV fo Foy, and Mixture 1, where (11"]=0.025 mol dm~* was also iept constant, and "086 mV in Fy and Mixture 2, where the [C3] (1.050 mot dm was also Kept constant” The composition of the species formed in ByIL,, where Bi the central metal on end Ls the igand. The systematic ereos ih he equiibrium constants (og B,,) have been estimated caused by the Systematic errors in Ey) This work is Part 4 of a series. The earlier parts are presented in Refs. 1-3, In Ref. 1, potential functions were derived for the calculation of potentials across liguid junctions of constant ionic medium types, for emf. cells! containing mixtures of strong electrolytes with the junction type AY|AY +BY.) +HY under the experimental conditions that (A*]=C mol dm”? is con- stant, [Y-]=Cmol dm”*is constant and /=Cmol dm~? is constant, For the calculation of the total potential anomalies in these cells, the ionic molar conductivities are needed for every electrolyte mixture studied, Definitions and symbols used throughout this series are also presented in Ref. 1 Tonic molar conductivities have been determined in the mixtures of Cd(CIO,), + HCIO,+NaClO, under the experimental conditions that [Na*]=3 mol dm~* is kept constant (Ref. 2) and [Y"]=3 mol dm~*is kept constant (Ref. 3). The influence of the neglection of the liquid junction potential terms on the equilibrium constants studied (log By.) has also been discussed? In the present part, the ionic molar conductivities will be estimated in the electrolyte mixtures given above, under the experimental condition that = C mol dm”? is (© Ata Chemica Scandinavcs $3 (1995) 1-6 kept constant. The constants of the Nernst equation, Foy and Ey, are determined in e.m.f. cells containing these mixtures. The total cell exm.f. for these cells studied can be given as Ey= Eoy + (8/23) 108 cs frrsa + Eo + Eve (ia) The total potential anomalies in the cells are ‘AE, = (8/25) log frsz + Ev + Eor (ab) In the present practice, conditional constants are deter- ined! in the e.m.f. cells Ena = Eon + 80nd (ey in Mixture 1, as an intercept of the plot Zy~(g/zx) log ¢y versus ¢, at constant ¢. Moreover, Eoux= Fou + ands (aa) in Mixture 2, as an intercept of the plot £y~g log cx versus cy at constant cy. The composition of these mixtures is given below. Here, the terms d; and dy are functions! with constant values, in terms of some ionic molar conductivities and interaction coefficients. In studies of complex formation reactions through NEMER-NEUMANN emf, cells, the constants Foy and Foy are needed, ‘Therefore, the systematic errors geyds and geyds Must be determined, ‘The composition of the mixtures studied was as follows. Mixture 1: cj.=0.025 mol dm™?, is kept constant, ¢y is varied within the range 0-0.1 moldm~*, X mol dm-* AY under the experimental condition that /= 3 mol dm”*, constant. Mixture 2: cq =0.050 mol dm”, is kept constant, cy is varied within’ the range 3%10~2-0.1 mol dm” 3," mol dm™? AY under the experimental condition that /= 3 mol dm” is constant Here, B=Cd?*, Yo=ClOy, A ey=(H']=(HCIO,) mol dm [Ca(C10,)shroras. mol dm ‘The ionie strength in these mixtures ean be given, with the concentration condition ey =2aca+ cy +Eq. aS Na’ and n= (Cd? }= Tey-teqt each 29)/2=C mol dm? i) Moreover, for the ion concentrations ¢, and ey we have = Ce — 6B + 29/2 mol dm~? AY @ v2 a y= C+ Zncy~ Ooh + Estimation of the ionic molar conductivities ‘The conductivity measurements have been carried out as described in Ref. 2 In this section, all molar conductivities (A. and A) are expressed in Sem? (g mol)~* and the conductivity (x) in Sem” units, and are generally omitted in the text for simplicity. 1. Conduetivity measurements in. mixtures where ey is varied while cy is kept constant. ‘The conductivity 10° « was measured in Mixture 1. These data have been interpreted in terms of the ionic molar conductivities 2s, Mis Inu and dy. The interpretation of the data was done with the help of several plots as presented below. A similar treatment has already been used in Ref. 2, where the same system was studied under the experi- ‘mental condition that {Na*]=3 mol dm” is constant. Here, tr denotes trace. 1.1. The percentage deviations of the conductivity from additivity. The data were plotted as 107 (10° «10? Kyga)/ 10° versus ¢y. Here, 10° stands for the measured conductivity of the solution studied and 10° x,aq is ealcu- lated according to the additivity, in the same way as shown in Ref. 2 (ef. eqns. (17)-(19)]. This plot is given in Fig. 1. As is seen, the deviation function is linear, positive and at around [Cd?*]=0.1 mol dm~> reaches 6%. ‘This mixture shows the highest deviation from additivity among all the mixtures of Cd(CIO,)3+ HCIO,+NaCiO, which were studied by the author. 1.2. The plot 10° x versus [Cil** ] at ey =0.025 mol dm”, constant, This plot is presented in Fig. 2 and gives the ——— FE wean Fig. 1. The deviation of the measured conductivity (10° x) from additivity (10° kag), in %, 38 3 function of {Ca2"), in the system 0.025 M HCIO,, 0<{Cd(CIO4)_]<0.1 M and XM [NaCiOg, using /=3M, constant, at 25.000 + 0.008 °C. a Oe Fig. 2. 10? x versus (Cd? for the determination ofthe ionic molar conductivities in the system 0.025 M_ HCIO,, O<{CéKCIO¢)g}<0.1M and X'M NaCIO,, using 1=3M, con. stant, at 25.000:+0.005 C. measured data without transformation, The fundamental equation, which is valid here, is 10? «= 2yeahih endif + LY Poy +1A Pa w Here, hy is the function of the composition of the tet solution. For this plot wh + Poa Y1-+ RAIA (6) which is equal to 168,88 in experiment 1 and 169.33 in experiment 2. The intercept represents the conductivity ‘of the two-component system 0.025 M HCI, +2.975 M NaClO,, First, we can estimate the ionic molar conduct. ivties valid in'this system. Here, iy, can be considered as constant, being equal to the value valid in 3M NaCiO,. We assume that the ionic molar conductivity of the ClO,~ ions in this two- component system, yay canbe ealeulated due to additvity ff. qn. (19) in Ref. 2} in terms of the ionic strength fractions. Therefore, we have aug = 043 X 54,60 = 23.48 the intercept © JONIC MOLAR CONDUCTIVITIES IN Calc dy (3M NaClO,) = 0.57 x 54.60 dy (3M HCIO,) = 0.17 x 233.1 Hence, 2jj can be obtained from the intercept = 168.88 Ajay = 218.28 AAs is seen, 2 is slightly higher than its value in 3M HCIO,: dy (3 M_HCIO,)=0.83 x 233.1=193.5. This result is consistent with the positive intercept of the straight line obtained for the percentage deviation curve. ‘Here, the transport numbers and the molar conductivities for 3M NaClO, and 3M HCIO,, determined by Biedermann and Douhéret,* were taken from Ref. 1 A small uncertainty in the position of the intercept strongly influence the value of Aj, as discussed in Ref. 2 In order to estimate the magnitude of this uncertainty, we shall consider the value of 10°x, measured in Mixture I and Mixture 2 (to be discussed in Section 2.2) at the common experimental point [H*]=0.025 M and [Ca?*]=0.050 M. These two values should be identical AL this composition we have Mixture 1 Mixture 2 10% 166,93 (in expt. 1) 10" 167.27 in expt. 2) 167.20 Here, expt. denotes experiment. According to this com- parison, —0.27 unit total uncertainty (0.18%) appears between the corresponding 10*x values for Mixture 1, expt. 1, and Mixture 2, due to some uncertainty in the position of the intercept in Fig, 2. Therefore, we choose expt. 2 as the correct one. Thus we take the intercept of expt. 2 (169.300.07) for the calculation of the final value of 2, from eqn. (5). Hence, we obtain ig) = 235.08 + 1.60 ‘The uncertainty in this result is 0.68% denotes result. 13. The plot of 10° x—[¥° Jayey versus [Cé**]. at [HCIO,]=0.025 M, constant. The value of 2 in this special mixture was estimated as follows. Inserting the special concentration condition given by eqn. (2) into eqn, (4) and forming the difference given in the title, we obtain 10 «-[Y Pon Here, R alzwhis — ha(ci + 20)/2] + cui ha) + hy o Here, Ay. denotes the values valid in the three-compon- cent system and calculated according to the additivity yy) ey (3M NaClO,)/1 + eyhy (3M HCIO,)/T Y2Pry (1.5 M Ca(C1O,)3)/F tea (8) ‘The values obtained change linearly with composition, according to dey) = 31.19 ~ 15.03 [Co] 0 J+ HCI0,+NaCiO, SOLUTIONS. ‘The molar conductivity of 1.5 M Cd(CIO,)2 was meas- ured by the author.? Moreover, the approximation fea [1.5 M Cd(C1O,)s introduced. The plot in question is shown in Fig, 3. Here, the slope is equal to HB —Ra(ch + 29)/2= 35.10 From this slope value we can calculate Nig = 52.77 As is seen, the Ca* ions are strongly accelerated in this rmixture. Therefore, the deviations are positive in Fig. 1 Having these results, we can check how the constancy of the ionic molar conductivities is fulfilled. As is seen, Dy, A and Ag ate constant, Ayes changes slightly with the composition of the test solution. ‘This mixture is generally used in Fp titrations where a B+ ion-sensitve indicator electrode is used. Here the potential function given below is valid." a Fn — (E2n) 1OB cw ay ‘The functions d, and dy are defined in Ref. 1 by eqns. (94) and (95). In this function, Ep, ratios ofthe following, ionic molar conductivities appear: Fon + Bde + Bsc, RB RW) = yy = 24 VI2.303 CR, + Ay) 3) Calculating these ratios at the beginning and at the end of the concentration range of the Cd” ions studied, we obtain the uncertainties given in Table 1. As it is seen from this table, the ratios of the ionic molar conductivit- ies in question are constant. However, the function obtained for the total cell exm.f. Ey, is very sensitive to small changes in the ratios of the ionic molar conduetivit- ies. The uncertainties in Ey, which appear due to changes in dys ate 0.13 m¥/M Ca", which gives 0.01 mV at 0.1 M [Cé?*], and 0.79 mV/M H*, which gives 0.02 mV 1 rorwezo ne, Sone eae Fig. 3. UICH*)=10° x-[Yinlhva) versus {Cé?*], for. the estimation of AZ, inthe “tystem 0.025 M_ HCIOy, O<{CdICIO4)2)<0.1M and XM NaCiOg, at /=3M, is kept constant, NEHER-NEUMANN Table 1, Estimation of the uncertainties |dE| in Ey {ct qn. (11), in mV/M Cé®” or H", caused by the change of Fy With the composition, cd?" in M: 7.679 x 10-* 99.508 «10°? 31.08 )y)> 29.70 ~0.0386'> A(B*) > “0.0334 ~2.10259.16A1B*") mV Limol Cd? > -197 dE qi mV Limmol Ca?" =0.13 0.5158 RiH")< 0.5292 ~ 30,52.<59.16R(H*) mV Lmol H* < 3131 [deg] mV Limol H” = 0.79 uncertainty at 0.025 M [HCIO,]. As is seen, the uncer- tainties are of the same order of magnitude as those of the most accurate e.m.f. measurements. Hence, the poten- I functions derived in Ref.1 are valid for these mixtures. 2. Conductivity measurements in mixtures where cy is varied and cy is kept constant. The conductivity 10° « has been measured in Mixture 2. These data have been interpreted in terms of the ionic molar conductivities BE, Mi. ha and Aya). The treatment of the data has been similar to that one used in Section 1 2.1. The percentage deviations of the conductivity from ‘additivity. The deviation function used in Section i.1 is plotted as a function of [11°] in Fig. 4. The deviations are positive, a linear function of (H*] and decrease. At (H"]=0 we have large positive deviation due to the increase of Af in this mixture, too. The small and negative slope shows that 24 is slightly lower than in 3M HClO, 2.2. The plot of 10° versus [H*] at [Ca{ClOu)2 0.050 M, constant. This plot is presented in Fig. 5 which isa straight line and gives the measured data without transformation, According to eqn. (4), the intercept of 2 Fonsaro ni be Fig. 4. The percentage deviation of the measured condue- tivity (10° x) from additivity (10° xg) as @ function of [H"], inthe system 0.050M CdiClOyy, ~2x 10-*<(HCIO,] 0.1M and X M NaCiO,, at /=3M, is kept constant, at 25.0000.005°C. Fe ee Fig. 8. 10% versus 1H", for the determination of the ionic ‘molar conductivities in the system 0.050™M Co(CiO4}, ~2%10-*<{HCIO,)<0.1 M and XM NaClO,, using =3™, Js kept constant, at 25.000 +0.005°C. this plot is cab +(A* ha + Mal aay This equation describes the conductivity of the two component system 0,050 M C4(CIO,)s, is kept constant, and 2.850 M NaCiO,. The intercept ean be used for the estimation of As, Mf) and 24. We can assume, again, that 2, has the same value as in 3M NaClO,. Moreover, 24, will be calculated as before. Hence, we have for this sYstem hy =23.48 and Af we can ealeulate from the intercept Au. ‘Again, a smal, possible uncertainty in the position of the intercept strongly influences the value of 2%. The uncertainty of the intercept in question was found to be £0.04 units, Hence, the following final result could be calculated: eam) = 66.31 £0.38 This corresponds to 0.57% uncertainty. 23. The plot of 10°x—-[Y" Jia versus [H*] at [Ca(ClO,) 2] =0.050 M, constant. The value of Hi valid in this mixture, has been estimated with the help of the plot given in the title and is presented in Fig. 6. On the basis ofthis plot, and eqn. (7), the slope is given by Dh — I = 156.43 as) From this, we can calculate 2 = 179.91 ‘The values of f, valid in the three-component system, have again been calculated due to the additivity. The values obtained can be described by the equation 2g) = 30.37 + 2.83 (H*] 6) ‘The slight change in these values with [H*] does not influence the constancy of the ratios R(B?*) and R(H*) which appear in the total cell em. By ff. eqns. (45), (95) and (96) in Ref. 1 IONIC MOLAR CONDUCTIVITIES IN Ca(CI0,), + HCIO,-+NeCIO, SOLUTIONS al Soser te 7 oa | Fig. 6. UH") =10° x—L¥iFoyg versus [H"), forthe estime- tion of Hin the system 6.050M CdlCIOy),, ~2x 10? SIHCIOI<0.1M and XM NaCiO,, at /=3M, is kept constant 3. Conductivity measurements in mixtures where both cy and Cy are varied. If both Egg and Ey are to be determined within one titration, then both cy and cy should be varied, For the calculation of AB,, the relevant 2, values must again be determined. The conductivity ‘must to be measured in a mixture of strong electrolytes, as suggested in Section 3 of Ref. 2. The measured conduc tivity data can be interpreted in terms of the ionie molar conductivities only with the help of a curve-fitting com- puter program, e.g. MLAB.° This can be done in a similar way as suggested in Refs. 2 and 3. In this treatment of the data, Ay) can be used for the ionic molar conductivity of the ClO,” ions. Expressing Ri in general as M=Si+(or -) free a7) wwe can transform the data into the following form: 10° = [Y Ry) — Cha = en beal fi + (or ~) fren) bach + 20)/2) + cua) cas) ‘on the basis of eqn. (7). Here, we can assume that Ays has the same value asin 3 M NaClO,. Now, the function Focaics Which consists of the right-hand side of eqn. (18), ccan be fitted to the data Foe, by adjusting f,, f, and Dif as parameters. Here, We can use hoy [15M Cd(CIO,),) as a starting value for f,. The subscript cale stands for calculated. Experimental details are. given in Ref. 2. Foes Discussion As is seen, the ionic molar conductivities (or some ratios of them) obtained here are constant. This was the most important condition of the deductions used for the calculations of the potential functions valid in e.m.f. cells with liquid junctions and contained mixtures of three strong electrolytes [ef. eqns. (1a) here and (40) and (45) in Ref. 1] Having these results, we can estimate the systematic errors in the conditional constants Foye and Foe Considering eqn. (Ie) here and eqn. (95) in Ret. 1, we can calculate the systematic error in Foye and Mixture 1 We obtain sendy = —0.71 mV Hence, we have Foy = Eoya + 0.71 mV Considering eqn. (Id), here and eqn. (96) in Ref. 1, we can calculate the systematic error in Egy, and Mixture 2. We obtain gendy= —0.86 mV Hence, we have Eau = Eoin + 0.86 mV ‘As is seen from these estimates, the systematic errors in Fog, and Eqy, are not negligible if we use a curves fiting treatment for the em. titration data, and the accuracy ofthe fitted function should be 0.01 mv. The systematic error geydh is a function of cy and causes the variation of the equilibrium constants studied (log Bygs) With cy, as is seen from Table 1 in Ref. 2. If the complexes B, HL, are formed, we have the following systematic errors it 1Og Bp For <(B)=2 ont seudsymV — p=l p=? pw Ey 0.11 0024 0.048 — —0.071 For 2(B)=3 Eon +gendsymV — p=l p= 2 ps3 Eng 0.71 =0036 -0.072 0.106 The systematic error gepdy is a function of cy and it ‘causes the variation of the equilibrium constants studied (log Bpgs) With cy, as is seen from Table 2 of Ref. 2. Hence, in the present case, we have the following system- atic errors? in log Bygr (Eou + gcuds)/mV q=l q Ex — 0.86 0014 0.029 ~0.043 The variation of log Bq, with cy and cy, respectively, ‘can be interpreted as the formation of polynuclear com= plexes, if we do not take into account the systematic errors in question, In Ref. 1, the potential contributions of the changing concentrations of the Cd?* and H* ions to the total potential anomalies in the cells were calculated, in order to prove the theory developed in Ref, 1. The calculated and measured slopes (defined in Ref. 1) agreed well. Slope/mV M~* SL(H, ¢y) SL(B, eg) SL(H, ¢y) SL(B, cy) Calculated 157-275-1980 19.80 Measured 16 0405 17.7 NEHER-NEUMANN Table 2. Estimation of the systematic errors in the formation constants 109 far. caused by the systematic (coll B) and ay (cell K) under different experimental conditions. crs in Eos Conditional constants mv cell B Coll H Mixture 1: ¢y=0.025 mol dm-* con. Mixture 2: ¢,=0.050 mol dm? con: stant stant Foon = Foot dont Eonn= Eon t 900d} Experimental conditions Systematic err0r8 in 10g Baar pat pe2 a2 a3 INa“1=3 M is kept constant? Systematic error mV in Eom: ode Eo OF Ey E199 A108 Bre 0036 0067 0.102 [10,_1=3 M is kept constant* Systematic errorm¥ in Eon: ghee =0.56 Eq oF Eu nV Fog 0.83, Fog 056 109 Baar 0017 0034 ~0.050 000se 0.016 0.028 for 218) 3M is kept constant Systematic errr/mV in Eos: adhey= —0.71 in Eom: gd}ea = —0.86 Egg oF EnV Fog £0.71 Fong 0.86 109 Paar “O24 0048-0071 “O01 —0.029 00043 for 218) =2 ‘This means that both the developed equations! and the < eee determined ionic molar conductivities are correct. 3M constant <[Na"}=3M constant. It should be pointed out that the real systematic errors At the experimental conditions [CIO,"]=3 M and J= in exm. cells with complex formation will be higher than end; and geyds, because the ions of the equilibrium solution will also contribute to the total potential anom- alies in the cells fef. eqns. (7) and (9) in Ref. 2 and Part 5"). Moreover, the potential functions of the total cell em. are different in cells containing the mixtures of strong electrolytes and in those containing equilibrium solutions, ‘We can compare the systematic errors in the formation constants, AlogB,.,, in cells B and H, containing Mixtures I and 2, under the three different experimental conditions studied and caused by the systematic errors, in Eoy and Foy. These are presented in Table 2. For cell B we obtained: los By, teglgible for 2(B) M constant <[C1O, M constant. at [Na‘] 3M constant

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