Very dilute solutions

If we consider solutions very dilute in alcohol and containing an excess of the active solute S then the alcohol will be present either as monomer or as AS complexes. Furthermore since cannot be greater than c, it can be neglected in comparison with so that (26.94) can be written approximately... 

Many of the reference half cells for electrochemical measurements are metals in contact with insoluble salts suspended in solutions very dilute in the metal ion and containing the anion causing precipitation at... 

In the absence of excess salts, accurate measurements can be made equally well on both very dilute and very concentrated solutions. Very dilute solutions, of course, must be protected from contamination by acidic or basic gases in the atmosphere. 

Some authors go further into approximations They assume that v Vo. This implies that the titrant solution is very concentrated and the titrand solution very diluted. In these eonditions, the titration curve equation before the equivalence point becomes... 

Debye-Hiickel theory The activity coefficient of an electrolyte depends markedly upon concentration. Jn dilute solutions, due to the Coulombic forces of attraction and repulsion, the ions tend to surround themselves with an atmosphere of oppositely charged ions. Debye and Hiickel showed that it was possible to explain the abnormal activity coefficients at least for very dilute solutions of electrolytes. 

A logical division is made for the adsorption of nonelectrolytes according to whether they are in dilute or concentrated solution. In dilute solutions, the treatment is very similar to that for gas adsorption, whereas in concentrated binary mixtures the role of the solvent becomes more explicit. An important class of adsorbed materials, self-assembling monolayers, are briefly reviewed along with an overview of the essential features of polymer adsorption. The adsorption of electrolytes is treated briefly, mainly in terms of the exchange of components in an electrical double layer. 

A special corrverrtion exists concerning the free errergies of ions in aqueous solution. Most themrodyrramic iirfomration about strong (fiilly dissociated) electrolytes in aqueous solutions comes, as has been seen, from measiiremerrts of the eirrf of reversible cells. Sirrce tire ions in very dilute solution (or in the hypothetical... 

It is important to recognize the approximations made here the electric field is supposed to be sulficiently small so that the equilibrium distribution of velocities of the ions is essentially undisturbed. We are also assuming that the we can use the relaxation approximation, and that the relaxation time r is independent of the ionic concentration and velocity. We shall see below that these approximations break down at higher ionic concentrations a primary reason for this is that ion-ion interactions begin to affect both x and F, as we shall see in more detail below. However, in very dilute solutions, the ion scattering will be dominated by solvent molecules, and in this limiting region A2.4.31 will be an adequate description. 

GivenyCr, r ) I for very dilute solutions, the PY condition leads to... 

Light scattering teclmiques play an important role in polymer characterization. In very dilute solution, where tire polymer chains are isolated from one anotlier, tire inverse of tire scattering function S (q) can be expressed in tire limit of vanishing scattering vector > 0 as 1121... 

Silicon and germanium readily react with even very dilute solutions of caustic alkali. Silicon is so sensitive to attack that it will dissolve when boiled with water which has been in contact with glass ... 

The sea water is first treated with chlorine in acid solution (sulphuric acid is added) and very dilute bromine is obtained by blowing air through the solution. This is mixed with sulphur dioxide and the gases passed up a tower down which water trickles ... 

Oxygen difluoride, OFj, is obtained when gaseous fluorine is passed through very dilute (27 ) caustic soda solution ... 

Reactions of Aspirin, (i) Distinction from Salicylic acid. Shake up with water in two clean test-tubes a few crystals of a) salicylic acid, (0) aspirin, a very dilute aqueous solution of each substance being thus obtained. Note that the addition of i drop of ferric chloride solution to (a) gives an immediate purple coloration, due to the free —OH group, whereas (b) gives no coloration if the aspirin is pure. 

Dissolve 0 3 ml. of glacial acetic acid in 2 ml. of water in a 25 ml. conical flask, and add 0 4 ml. (0 44 g.) of phenylhydrazine. Mix thoroughly to obtain a clear solution of phenylhydrazine acetate and then add 0 2 ml. (0 21 g.) of benzaldehyde. Cork the flask securely and shake the contents vigorously. A yellow crystalline mass of the hydrazone soon begins to separate. Allow to stand for 15 minutes, with occasional shaking, and then filter the solid product at the pump, wash first with very dilute acetic acid and then with water, and finally drain thoroughly. Recrystallise the material from rectified or methylated spirit, the benzaldehyde phenylhydrazone being thus obtained in fine colourless needles, m.p. 157 yield, 0 4 g. 

Reagent A is particularly useful for the treatment of the lower aliphatic aldehydes and ketones which are soluble in water cf. acetaldehyde, p. 342 acetone, p. 346). The Recent is a very dilute solution of the dinitrophenylhydrazine, and therefore is used more to detect the presence of a carbonyl group in a compound than to isolate sufficient of the hydrazone for effective recrystallisation and melting-point determination. 

The phenylarsonic acid should separate from the cold stirred solution within 10-20 minutes. If separation does not occur (due to the addition of too much acid), add a few drops of dilute aqueous sodium hydroxide and again bring the solution very carefully to the desired pH. 

NH2CONH2 = NH2CONHCONH2 + NH3 Dissolve the solid residue in a few ml. of warm 10% NaOH solution, cool and add i drop of very dilute copper sulphate solution. A purple coloration is obtained. ... 

Biuret test. Oxamide, having two CONHj groups, will give this test without any preliminary treatment (c/. urea). Shake o-i g. of oxamide with 1 ml, of 10% NaOH solution, add i drop of very dilute CuSO solution and mix well. A rose-pink coloration is produced. 

Microscope appearance. Place a small amount of dry starch on a microscope slide, add a drop of water, cover with a slip and examine under the microscope. Characteristic oval grains are seen which have concentric rings round a hilum which is towards one end of the grain. Run a drop of very dilute iodine solution under the slip from a fine dropping-tube the grains become blue. 

The colour reactions with the enzyme peroxidase and HjO permit all the above amines to be distinguished from one another in very dilute solution (P- 523)-... 

Sorensen s reaction. First read carefully the Estimation of Glycine, p. 463. Dissolve 0 2 g. of glycine in a few ml. of water in a test-tube A, add 2 drops of phenolphthalein and then very dilute NaOH solution drop by drop until the solution just turns pink. In a second test-tube B place 2 ml. of 40% formalin solution, add 2 drops of phenolphthalein solution and then the dil. NaOH solution until the solution just turns pink. Pour the contents of B into A and note the immediate decolorisation of the phenolphthalein, the solution now being acid. Observe also that several drops of dil. NaOH solution can now be added before the pink colour is restored. 

Benzylthiouronium salts. Add 0 5 g. of sulphanilic acid to 10 ml. of water and 5 ml. of 10% NaOH solution, zndgently warm the shaken mixture until a clear solution is obtained. Cool, add 1 drop of phenol-phthalein solution, and then add dilute HCl dropwise with shaking until the pink colour is just discharged. Now add very dilute NaOH solution until the pink colour yt/rZ returns. Cool and add with shaking a solution of 0-5 g. of benzylthiouronium chloride in 5 ml. of water. The thiouronium salt rapidly separates filter at the pump, wash with water, drain and recrystallise from ethanol. Colourless crystals, m.p. 185°. (M.ps., p. 548.)... 

Methyl iodide, ethyl bromide and ethyl iodide also evolve small amounts of ethylene when treated as above. If this is suspected, a small quantity of the substance should be heated with alcoholic NaOH solution in a small flask, fitted with a knee delivery-tube. Pass the gas evolved through a very dilute solution of KMn04 which has been made alkaline with aqueous NagCOj solution. If ethylene has been formed, a brown precipitate of MnOj will be produced (a transient green colour may appear). 

Dissolve about 0 2 g. of urea in 5 ml. of water, add about 5 drops of phenohred and 1 drop of dil. HCl the colour is now yellow- Divide the solution into two portions. To one portion, add very dilute (about 1%) NaOH solution until the colour is r now add the second portion, drop by dropf until the red colour is just discharged. The solution is now at about pH y. 

Do not heat the silver solution or allow it to stand even for a few hours, since explosive silver fulminate may be formed. The ammoniacal solution of silver nitrate is prepared by treating 3 ml. of 0-lN silver nitrate solution with very dilute ammonia solution dropwise until the precipitate which is first formed just redissolves. 

Dissolve or suspend 0 - 5 g. of the acid in 5 ml. of water in a small conical flask, add a drop or two of phenolphthalein indicator, and then 4-5 per cent, sodium hydroxide solution until the acid is just neutrahsed. Add a few drops of very dilute hydrochloric acid so that the final solution is faintly acid (litmus).f Introduce 0-5 g. of p-bromophenacyl bromide (m.p. 109°) dissolved in 5 ml. of rectified (or methylated) spirit, and heat the mixture under reflux for 1 hour if the mixture is not homogeneous at the boiling point or a solid separates out, add just sufficient alcohol to produce homogeneity. [Di- and tri-basic acids require proportionately larger amounts of the reagent and longer refluxing periods.] Allow the solution to cool, filter the separated crystals at the pump, wash with a little alcohol and then with water. Recrystallise from dilute alcohol dissolve the solid in hot alcohol, add hot water until a turbidity just results, clear the latter with a few drops of alcohol, and allow to cool. Acetone may sometimes be employed for recrystallisation. 

The latter may be identified by dissolving the residue in 5 ml. of water and adding 1 op of very dilute copper sulphate solution and 2 drops of 10 per cent, sodium hydroxide solution a violet colour is produced. 

---