分析化学
分析化學
분석화학
CHINESE JOURNAL OF ANALYTICAL CHEMISTRY
2001年
1期
1-5
,共5页
张养军%张维平%高娟%耿信笃
張養軍%張維平%高娟%耿信篤
장양군%장유평%고연%경신독
反相高效液相色谱%计量置换保留模型%保留机理%同系物%流动相%脂肪酸
反相高效液相色譜%計量置換保留模型%保留機理%同繫物%流動相%脂肪痠
반상고효액상색보%계량치환보류모형%보류궤리%동계물%류동상%지방산
在反相液相色谱(RPLC)中用Snyder经验方程和计量置换保留模型(SDM-R)中的参数对溶质为脂肪醇同系物,流动相为脂肪酸同系物时溶质的保留行为进行了研究,结果表明用SDM-R参数具有明显的优越性。另外,由于用Snyder经验公式中二参数之间的作图无法准确求得斜率,且其不具有明确的物理意义,而由SDM-R二参数作图,不但能准确求得斜率j(与1 mol溶剂和固定相结合能有关的常数),而且j具有明确的物理意义并符合碳数规律,所以,参数j有可能用于RPLC中表征溶剂强度。由此得出,在RPLC中,对同一置换剂而言,随同系物溶质的Z(1 mol溶剂化溶质被溶剂化固定相吸附时,从二者接触面释放出的置换剂分子数)和logI(与1 mol溶质和固定相亲和势有关的常数)值增大,它们的保留时间也增大;对同一溶质而言,随着在同系物置换剂中碳链的增长,Z和logI值的减小,它的保留时间也缩短。同时还可得出,随着同系物置换剂j值的减小,它们的洗脱能力也增强。
在反相液相色譜(RPLC)中用Snyder經驗方程和計量置換保留模型(SDM-R)中的參數對溶質為脂肪醇同繫物,流動相為脂肪痠同繫物時溶質的保留行為進行瞭研究,結果錶明用SDM-R參數具有明顯的優越性。另外,由于用Snyder經驗公式中二參數之間的作圖無法準確求得斜率,且其不具有明確的物理意義,而由SDM-R二參數作圖,不但能準確求得斜率j(與1 mol溶劑和固定相結閤能有關的常數),而且j具有明確的物理意義併符閤碳數規律,所以,參數j有可能用于RPLC中錶徵溶劑彊度。由此得齣,在RPLC中,對同一置換劑而言,隨同繫物溶質的Z(1 mol溶劑化溶質被溶劑化固定相吸附時,從二者接觸麵釋放齣的置換劑分子數)和logI(與1 mol溶質和固定相親和勢有關的常數)值增大,它們的保留時間也增大;對同一溶質而言,隨著在同繫物置換劑中碳鏈的增長,Z和logI值的減小,它的保留時間也縮短。同時還可得齣,隨著同繫物置換劑j值的減小,它們的洗脫能力也增彊。
재반상액상색보(RPLC)중용Snyder경험방정화계량치환보류모형(SDM-R)중적삼수대용질위지방순동계물,류동상위지방산동계물시용질적보류행위진행료연구,결과표명용SDM-R삼수구유명현적우월성。령외,유우용Snyder경험공식중이삼수지간적작도무법준학구득사솔,차기불구유명학적물리의의,이유SDM-R이삼수작도,불단능준학구득사솔j(여1 mol용제화고정상결합능유관적상수),이차j구유명학적물리의의병부합탄수규률,소이,삼수j유가능용우RPLC중표정용제강도。유차득출,재RPLC중,대동일치환제이언,수동계물용질적Z(1 mol용제화용질피용제화고정상흡부시,종이자접촉면석방출적치환제분자수)화logI(여1 mol용질화고정상친화세유관적상수)치증대,타문적보류시간야증대;대동일용질이언,수착재동계물치환제중탄련적증장,Z화logI치적감소,타적보류시간야축단。동시환가득출,수착동계물치환제j치적감소,타문적세탈능력야증강。
The retention behaviours of n-aliphatic alcohols with mobilephase of n-aliphatic acids-water in reversed-phase liquid chromatography (RPLC) were studied with stoichiometric displacement model for retention (SDM-R) and Snyder′s empirical equation. The results obtained showed that SDM-R was superior to Snyder′s empirical equation when they were employed to characterize the retention behaviours of homologue and the solvent strength of homologous displacers. The slope, 1/q, of the plot of logK0w versus S has no clear physical meaning and can not be measured accurately, while the slope, j (a constant relating to the affinity of 1 mole solvent to bonded stationary phase ), of the plot of logI (a constant relating to the affinity of 1 mole of solute to bonded stationary phase) versus Z (the number of solvent molecules released from the contact surface region of 1 mole of solvated solute absorbed onto solvated bonded stationary phase) is not only determined accurately but also has a clear physical meaning and follows the rule of carbon number. Therefore, if it is possible, j can be used to characterize the solvent strength employed in RPLC. The conclusion is that with a given displacer, the retention of homologue in RPLC increases with their Z and logI increasing. If a solute is given, with the increment in carbon chain of homologous displacers, the values of Z and logI of the solute decrease and thus lead to the decrease of the solute retention, and the elution strength of a solvent becomes strong as the j value of a homologous displacer becomes small.