CS224919B1 - The membrane for the baryum ion selective electrode - Google Patents

Description

The invention relates to a membrane for a barium ion selective electrode, or more specifically a ligand, which is part of a complex forming the active ingredient of the membrane.

One of the more recent types of ion-selective electrodes that have recently appeared in the literature and also on the market is the barium ion-selective electrode. Simon and colleagues have been involved in the preparation of this type of electrode based on oligoglycolic acid derivatives. He used tetraglycolic acid bis-diphenylamide as a complexing lignad for these sensors, which formed a complex corresponding to the schematic formula. Ba. (SCN) ₂ , wherein L is a ligand, tetraglycolic acid bis-diphenylamide,

Ba is a barium cation and a SCN sulfocyanide anion.

Compared to the known, they exhibit improved membrane properties for a barium ion selective electrode comprising an active complex salt of the schematic formula Lg where Ba is a barium cation, Σ is a lipophilic anion such as tetrafenylborate or tetra- (p-chlorophenyl) borate anion that, as ligand I is used tetraglykolové acid derivative and N, N ^Z - diphenyl-N, N'-di (2-ethoxycarbonyl-phenyl) diamide 3 6 »-trioxáunděkandiově 3, of the formula

-ι

C

C00.C ₂ H ₅

COO.C ₂ H ₅

Example 1 _{224 gig}

A membrane for a barium ion selective electrode containing the L ₂ complex was prepared. Ba * (X) ₂ , wherein 1 is a ligand according to the invention, i.e. N, N ' -diphenyl-NN ^from 3,6-8-trioxaundacanedioic acid di (2-ethoxycarbonylphenyl) diamide, Ba barium cation X lipophilic anotite in in this case an anionitetrafenylborate. The membrane had the following overall composition:

polyvinyl chloride complex

1.36% wt.

30.61% wt.

2,4-dinitrophenyl-n-octyl ether 68,03% w / w,

For membranes of this composition were manufactured with an inner referentním solution _with 0. .I mol / X BaClg and internal reference electrode of Ag / AgCl.

These electrodes were measured at 293 µl 1 ° K using the cell: barium ion selective electrode of the invention / saturated calomel electrode.

The response of the electrode to the activity of the memorized ions was measured in the solutions of memorized chloride over a concentration range of 10 ^ to 10 ^{1 1} mol / l.

The results are

-Λ listed in Table I

224 919 Table I

^c BaCl ₂ as ^"01/1) EMS (mV) 10 ” ⁶ -98.4 10 “ ⁵ -70.5 10 “ ⁴ -43.0 10 “ ³ -15.6 10 ~ ² + 9,5 10 “ ¹ +31.9

Δ EMS (mV)

27.9

27.5

27.4 25.1

22.4 ° • Pot ^K Ba, j 0.1 mol / l are passed

Furthermore, the selectivity coefficients were measured by a separate sample method, using chloride solutions of the respective cations. Values

Pot 'in Table II. in the form of log Κ X..

M, J · Table 11

log ^The Ba Li - 3,39 log ^K Ba, KH ₄ - 3,79 log ^K Ba, Na - 3,01 log ^K Ba, Mg - 6,46 log ^K Ba, K - 2,92 log ^K Ba, Ca - 3,13 log ^K Ba, Rb - 3,21 log ^K Ba, Sr - 0.98 log ^K Ba, Cs - 3,10

Example 2

Similar to Example 1, membranes were made except that tetra- (p-chlorophenyl) -borate anion was used as lipophilic anion X and the membrane had an overall composition:

polyvinyl chloride complex

2,4-dinitrophenyln-octyl ether

1.69% wt. 30.51% wt.

67.80 wt.

Here too, as in Example 1, the electrode response to bamboo ion activity was measured, and the results are shown in Table III. and measured selectivity coefficients ^K Ba ^ J ^{'where the sequence} characterized as alkyl log are shown in Table IV.

Table III

° BaCl ₂ EMS (mV) l ₀ -6 10-5 - 100.9 IO ' ⁴ 72.0 IO ³ - 43.8 IO ' ² - 17,0 IO ' ¹ + 6.7 + 29.7

Table IV

224 919 BT.5 (mV)

28.9

28.2

26.8

23.7

23.0

^{log K} Ba, Li - 3,55 ^l0g ¾a, Na - 3,01 ^log ^ Ba, K. - 2,34 ^{10g K} Ba, Rb - 2,35 ^log ^ a, Cs - 2,14

^{log K} Ba, NH ₄ “3,17 ^{10g K} Ba, Mg - 6.23 ^log Ba, Ca - 2,60 ^log Ba Ba, Sr - 1,42

Claims (1)

A barium ion selective electrode membrane comprising an active complex sol of the schematic formula wherein Ba is a barium cation, X is a lipophilic anion such as tetrafenylborate or tetra- (p-chlorophenyl) -borate anion, characterized in that an acid derivative is used as ligand I » 3,6,9-trioxaundecanedioic acid N, N'-diphnyl-N, N'-di (2-ethoxycarbonylphenyl) -diaminde of formula (X)