Sodium equilibria

The excitable membrane of nerve axons, like the membrane of cardiac muscle (see Chapter 14) and neuronal cell bodies (see Chapter 21), maintains a resting transmembrane potential of -90 to -60 mV. During excitation, the sodium channels open, and a fast inward sodium current quickly depolarizes the membrane toward the sodium equilibrium potential (+40 mV). As a result of this depolarization process, the sodium channels close (inactivate) and potassium channels open. The outward flow of potassium repolarizes the membrane toward the potassium equilibrium potential (about -95 mV) repolarization returns the sodium channels to the rested state with a characteristic recovery time that determines the refractory period. The transmembrane ionic gradients are maintained by the sodium pump. These ionic fluxes are similar to, but simpler than, those in heart muscle, and local anesthetics have similar effects in both tissues. 

Figure 7.6 Current-voltage relationship for passive channel models of Equations (7.27) and (7.28). Sodium concentrations typical for the squid giant axon are used [Na+ ] = 437 mM [Na J = 50 mM. The sodium equilibrium potential is VNa = 58.5 mV. Conductance g a is set to 0.01 mS-cm-2. The permeability for the GHK model of Equation (7.28) is set so that both models predict the same current density at AT = 0. Figure adapted from [108],...

If a membrane is permeable only to Na ions, then at equilibrium the measured electric potential across the membrane equals the sodium equilibrium potential in volts, iiNa-The magnitude of is given by the Nernst equation, which is derived from basic principles of physical chemistry ... 

It is also commonly considered that the low membrane potential of non-excitable cells arises from a near equality of the sodium and potassium permeabilities setting its value near the midpoint of the potassium and sodium equilibrium potentials. The membranes of many animal cells are highly permeable to Cl, and so according to the diffusion model this must also make an important contribution to the membrane potential. 

Brunauer and co-workers [129, 130] found values of of 1310, 1180, and 386 ergs/cm for CaO, Ca(OH)2 and tobermorite (a calcium silicate hydrate). Jura and Garland [131] reported a value of 1040 ergs/cm for magnesium oxide. Patterson and coworkers [132] used fractionated sodium chloride particles prepared by a volatilization method to find that the surface contribution to the low-temperature heat capacity varied approximately in proportion to the area determined by gas adsorption. Questions of equilibrium arise in these and adsorption studies on finely divided surfaces as discussed in Section X-3. 

Bloor D M, Wan-Yunis W M Z, Wan-Badhi W A, Li Y, Hoizwarth J F and Wyn-Jones E 1995 Equilibrium and kinetio studies assooiated with the binding of sodium dodeoyl sulfate to the polymers poly(propylene oxide) and ethyl-(hydroxyethyl)oellulose Langmuir 3395-400... 

The addition of the sulphuric acid first neutralises the sodium hydroxide, and then gives a weakly acidic and therefore colourless solution. The sodium derivative (A) then undergoes further partial hydrolysis in order to re-establish the original equilibrium, and the sodium hydroxide thus formed again produces the pink coloration, which increases in depth as the hydrolysis proceeds. 

Method 2 (E. L. Smith, 1927). Sodium alone cannot be used for the complete removal of water in ethyl alcohol owing to the equilibrium between the resulting sodium hydroxide and ethyl alcohol ... 

S4 °j760 mm.) is employed to remove all the sodium hydroxide in the equilibrium of equation (3) ... 

The equilibrium of the last step (3), which is not actually part of the condensation mechanism, is far to the right because of the greater basic strength of the ethoxide ion as compared to (IV), and this largely assists the forward reactions in (1) and (2). The reaction mixture contains the sodium derivative of the keto-ester, and the free ester is obtained upon acidification. 

However, if an oxidising agent (fuming nitric acid or sodium persulphate) is present to destroy the hydrogen iodide as it is formed, the equilibrium is displaced and the iodo compound may be conveniently prepared, for example ... 

Because of the great solubility of sulphonic acids in water and the consequent difficulty in crystallisation, the free sulphonic adds are not usually isolated but are converted directly into the sodium salts. The simplest procedure is partly to neutralise the reaction mixture (say, with solid sodium bicarbonate) and then to pour it into water and add excess of sodium chloride. An equilibrium is set up, for example ... 

The equilibrium of the overall reaction Is shifted in the direction of the condensation product by the precipitation of the p diketone as its sodium salt. 

In the above reaction one molecular proportion of sodium ethoxide is employed this is Michael s original method for conducting the reaction, which is reversible and particularly so under these conditions, and in certain circumstances may lead to apparently abnormal results. With smaller amounts of sodium alkoxide (1/5 mol or so the so-called catal3rtic method) or in the presence of secondary amines, the equilibrium is usually more on the side of the adduct, and good yields of adducts are frequently obtained. An example of the Michael addition of the latter type is to be found in the formation of ethyl propane-1 1 3 3 tetracarboxylate (II) from formaldehyde and ethyl malonate in the presence of diethylamine. Ethyl methylene-malonate (I) is formed intermediately by the simple Knoevenagel reaction and this Is followed by the Michael addition. Acid hydrolysis of (II) gives glutaric acid (III). 

The ketone is added to a large excess of a strong base at low temperature, usually LDA in THF at -78 °C. The more acidic and less sterically hindered proton is removed in a kineti-cally controlled reaction. The equilibrium with a thermodynamically more stable enolate (generally the one which is more stabilized by substituents) is only reached very slowly (H.O. House, 1977), and the kinetic enolates may be trapped and isolated as silyl enol ethers (J.K. Rasmussen, 1977 H.O. House, 1969). If, on the other hand, a weak acid is added to the solution, e.g. an excess of the non-ionized ketone or a non-nucleophilic alcohol such as cert-butanol, then the tautomeric enolate is preferentially formed (stabilized mostly by hyperconjugation effects). The rate of approach to equilibrium is particularly slow with lithium as the counterion and much faster with potassium or sodium. 

Charge diagrams suggest that the 2-amino-5-halothiazoles are less sensitive to nucleophilic attack on 5-position than their thiazole counterpart. Recent kinetic data on this reactivity however, show, that this expectation is not fulfilled (67) the ratio fc.. bron.c.-2-am.noih.azoie/ -biomoth.azoie O"" (reaction with sodium methoxide) emphasizes the very unusual amino activation to nucleophilic substitution. The reason of this activation could lie in the protomeric equilibrium, the reactive species being either under protomeric form 2 or 3 (General Introduction to Protomeric Thiazoles). The reactivity of halothiazoles should, however, be reinvestigated under the point of view of the mechanism (1690). 

The thiazolium is not acidic enough for observing directly solvation of the molecule (or an hydrolysis and subsequent cleavage of the ring) (24) without adding a base, as it is the case for benzoxazolium or benzothiazolium. With the same dilution (10 mole liter ), it is necessary to add sodium ethylate to the solution of 2-methyl-4.5-diphenylthiazolium to observe the equilibrium described above. A new band appears in the UV spectrum at 320 nm that is attributed to the ethoxy derivative by analogy to what has been observed with other benzothiazoliums (26),... 

If a solution of acetic acid at equilibrium is disturbed by adding sodium acetate, the [CHaCOO-] increases, suggesting an apparent increase in the value of K. Since Ka must remain constant, however, the concentration of all three species in equation 6.26 must change in a fashion that restores to its original value. In this case, equilibrium is reestablished by the partial reaction of CHaCOO and HaO+ to produce additional CHaCOOH. 

The observation that a system at equilibrium responds to a stress by reequilibrating in a manner that diminishes the stress, is formalized as Le Chatelier s principle. One of the most common stresses that we can apply to a reaction at equilibrium is to change the concentration of a reactant or product. We already have seen, in the case of sodium acetate and acetic acid, that adding a product to a reaction mixture at equilibrium converts a portion of the products to reactants. In this instance, we disturb the equilibrium by adding a product, and the stress is diminished by partially reacting the excess product. Adding acetic acid has the opposite effect, partially converting the excess acetic acid to acetate. 

A mixture of acetic acid and sodium acetate is one example of an acid/base buffer. The equilibrium position of the buffer is governed by the reaction... 

Suppose you need to prepare a buffer with a pH of 9.36. Using the Henderson-Hasselbalch equation, you calculate the amounts of acetic acid and sodium acetate needed and prepare the buffer. When you measure the pH, however, you find that it is 9.25. If you have been careful in your calculations and measurements, what can account for the difference between the obtained and expected pHs In this section, we will examine an important limitation to our use of equilibrium constants and learn how this limitation can be corrected. 

Analogously, aldehydes react with ammonia [7664-41-7] or primary amines to form Schiff bases. Subsequent reduction produces a new amine. The addition of hydrogen cyanide [74-90-8] sodium bisulfite [7631-90-5] amines, alcohols, or thiols to the carbonyl group usually requires the presence of a catalyst to assist in reaching the desired equilibrium product. 

A. C. Wittiagham, iLiquid Sodium—Hydrogen System Equilibrium and Kinetic Measurements in t/je 610—667 K Temperature Range, NTIS Accession No. 

AH (A)-menthol is made by synthetic methods. One method involves the cyclization of (+)-citroneIlal (68). Using a mild acid catalyst, (+)-citroneIlal [2385-77-5] undergoes an ene-reaction to produce a mixture of isopulegols (142). Catalytic hydrogenation of the isopulegol mixture gives a mixture of menthol and its isomers. The (A)-menthol is obtained after efficient fractional distillation and the remaining isomers can be equilibrated, usually with sodium menthol ate or aluminum isopropoxide. An equilibrium mixture is obtained, comprised of 62 wt % (A)-menthol, 23 wt % (+)-neomenthol, 12 wt % (+)-isomenthol, and 3 wt % (+)-neoisomenthol. The equilibrium mixture can be distilled to recover additional (+)-mentbol. 

In accordance with observations in halodinitrobenzene derivatives, fluoropyrazines are by far the most reactive of the halopyrazines. Fluoropyrazine undergoes facile reaction with sodium azide to give azidopyrazine (27), which exists in dynamic equilibrium with tetrazolo[l,5-a]pyrazine (28) (66JHC435). 

Reduction of indolenines with sodium and ethanol gives indolines. The pentachloropyr-role, obtained by chlorination of pyrrole with sulfuryl chloride at room temperature in anhydrous ether, was shown by spectroscopic methods to have an a-pyrrolenine (2H-pyrrole) structure (222). It is necessary, however, to postulate that it is in equilibrium with small but finite amounts of the isomeric /3-pyrrolenine form (3//-pyrrole 223), since pentachloropyrrole functions as a 2-aza- rather than as a 1-aza-butadiene in forming a cycloadduct (224) with styrene (80JOC435). Pentachloropyrrole acts as a dienophile in its reaction with cyclopentadiene via its ene moiety (81JOC3036). 

Cyclohexyl[l 5]crown-5, potassium complex equilibrium constant, 7, 742 (73MI52101) Cyclohexyl[15]crown-5, sodium complex equilibrium constant, 7, 742 (73MI52101) Cycloocta[ 1,2-c 5,6-c ]difuran H NMR. 4. 564 (70JA973) Cyclopenta[h][2.2.4]cyclazine... 

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