<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">JASMI</journal-id><journal-title-group><journal-title>Journal of Analytical Sciences, Methods and Instrumentation</journal-title></journal-title-group><issn pub-type="epub">2164-2745</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/jasmi.2014.41004</article-id><article-id pub-id-type="publisher-id">JASMI-44200</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Chemistry&amp;Materials Science</subject></subj-group></article-categories><title-group><article-title>
 
 
  Inflection Points on Some S-Shaped Curves
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>nna</surname><given-names>M. Michałowska-Kaczmarczyk</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Tadeusz</surname><given-names>Michałowski</given-names></name><xref ref-type="aff" rid="aff2"><sup>2</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Agustin</surname><given-names>G. Asuero</given-names></name><xref ref-type="aff" rid="aff3"><sup>3</sup></xref></contrib></contrib-group><aff id="aff3"><addr-line>Department of Analyti?cal Chemistry, The University of Seville, Seville, Spain </addr-line></aff><aff id="aff1"><addr-line>Department of Oncology, The University Hospital in Cracow, Cracow, Poland</addr-line></aff><aff id="aff2"><addr-line>Faculty of Engineering and Chemi?cal Technology, Technical University of Cracow, Cracow, Poland </addr-line></aff><pub-date pub-type="epub"><day>10</day><month>03</month><year>2014</year></pub-date><volume>04</volume><issue>01</issue><fpage>27</fpage><lpage>30</lpage><history><date date-type="received"><day>9</day>	<month>December</month>	<year>2013</year></date><date date-type="rev-recd"><day>9</day>	<month>January</month>	<year>2014</year>	</date><date date-type="accepted"><day>15</day>	<month>January</month>	<year>2014</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
   This paper refers to inflection point—the fundamental property of S-shaped curves. In this paper, the inflection points are related to pH titration curve pH = pH(V), and to the curve s = s(pH) involved with surface tension, s. 
 
</p></abstract><kwd-group><kwd>pH Titration; Surface Tension</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>This paper recalls the well-known property of different functions represented by the curves with sigmoidal shape (S-shape) [<xref ref-type="bibr" rid="scirp.44200-ref1">1</xref>] , involved with in&#173;flection (inf) point. An inflection point is the point on 2D plane where the curvature of the curve changes direction. The S-shape is characteristic, among others, for potentiometric titration curves [<xref ref-type="bibr" rid="scirp.44200-ref2">2</xref>] . Different methods of equivalence (eq) point determination are based on location of the inflec&#173;tion point on the curves pH = pH(V) or E = E(V), where E—potential, V—volume of titrant added. The inflection points are registered also in different physicochemical studies.</p><p>Generalizing, we refer to a monotonic function y = y(x). The inflection point (x<sub>inf</sub>, y<sub>inf</sub>) corresponds to maximal slope<inline-formula><inline-graphic xlink:href="tmlimages\4-1000127x\13a49286-75c4-4150-92fe-6878061986ba.png" xlink:type="simple"/></inline-formula>, where</p><disp-formula id="scirp.44200-formula89310"><label>(1)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\bb47df1b-5d22-4834-9928-ffcb27087470.png"  xlink:type="simple"/></disp-formula><p>Applying the relation</p><disp-formula id="scirp.44200-formula89311"><label>(2)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\a30ffe64-9f94-49d7-b167-139046d19e72.png"  xlink:type="simple"/></disp-formula><p>at the inflection point on the curve y = y(x) we have</p><disp-formula id="scirp.44200-formula89312"><label>(3)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\f48fbf34-99f8-4a07-b379-6840a84abb67.png"  xlink:type="simple"/></disp-formula><p>and then at dy/dx &#185; 0 we get</p><disp-formula id="scirp.44200-formula89313"><label>(4)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\ca766c88-6614-46c9-8001-b8ec6e1534d9.png"  xlink:type="simple"/></disp-formula><p>It means that the maximal slope is equivalent with the relation (4) valid for the inverse function x = x(y). This property is important for pH titration curves; namely, the functions V = V(pH) assume relatively simple form [<xref ref-type="bibr" rid="scirp.44200-ref3">3</xref>] .</p><p>In this paper, we refer to a simple acid-base ti&#173;tration (y = pH, x = V), and to the relationship s = s(pH) for surface tension (y = s, x = pH).</p></sec><sec id="s2"><title>2. Relation between Equivalence and Inflection Points in pH Titration</title><p>The main task of titration made for analytical purposes is the estimation of the equivalence vol&#173;ume (V<sub>eq</sub>). Let us consider the simplest case of titration of V<sub>0</sub> mL of C<sub>0</sub> mol/L HCl as titrand (D) with V mL of C mol/L NaOH as titrant (T). At V = V<sub>eq</sub>, the fraction titrated</p><disp-formula id="scirp.44200-formula89314"><label>(5)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\460fb47e-ac36-49bf-b454-8d7c1a7b7e9a.png"  xlink:type="simple"/></disp-formula><p>i.e., CV<sub>eq</sub> = C<sub>0</sub>V<sub>0</sub>. In this D+T system, the titration curve V = V(pH) has the form</p><disp-formula id="scirp.44200-formula89315"><label>(6)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\38843a89-1fc8-4693-a212-b887d0e06cae.png"  xlink:type="simple"/></disp-formula><p>where</p><disp-formula id="scirp.44200-formula89316"><label>(7)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\498ebedb-9790-427b-b8e9-cc1be89fdf97.png"  xlink:type="simple"/></disp-formula><p>To facilitate the calculations, it is advisable to re&#173;write (6) into the form</p><disp-formula id="scirp.44200-formula89317"><label>(8)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\13b24936-6353-4af9-8dd0-bccd81554777.png"  xlink:type="simple"/></disp-formula><p>From (5) and (6) we get</p><disp-formula id="scirp.44200-formula89318"><label>(9)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\ab6d3b8e-5318-42d3-9c4e-ee22b06ba56f.png"  xlink:type="simple"/></disp-formula><p>From (8)</p><p><img src="htmlimages\4-1000127x\234a4df7-262d-494d-9e59-6c633b2fa38b.png" /></p><disp-formula id="scirp.44200-formula89319"><label>(10)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\fefcc82c-f495-4842-b3c9-b37bdeea3d14.png"  xlink:type="simple"/></disp-formula><p>Setting d<sup>2</sup>V/dpH<sup>2</sup> = 0 and writing<inline-formula><inline-graphic xlink:href="tmlimages\4-1000127x\7f5b628e-7507-4fef-ae4c-5e5bd245cd80.png" xlink:type="simple"/></inline-formula>, from (10) we get, by turns,</p><disp-formula id="scirp.44200-formula89320"><label>(11)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\4431fad1-6bd7-4d1c-9398-e22f6bc8dfbe.png"  xlink:type="simple"/></disp-formula><p>From (11) we obtain for z = z<sub>inf</sub></p><disp-formula id="scirp.44200-formula89321"><label>(12)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\b3f85233-342f-430b-aed2-10ed75679cd9.png"  xlink:type="simple"/></disp-formula><p>and then for V = V<sub>inf</sub> [<xref ref-type="bibr" rid="scirp.44200-ref3">3</xref>] [<xref ref-type="bibr" rid="scirp.44200-ref4">4</xref>]</p><disp-formula id="scirp.44200-formula89322"><label>(13)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\95291d77-7230-482a-8f4d-7cd2b730759d.png"  xlink:type="simple"/></disp-formula><p>Analogous result can be obtained for titration of V<sub>0</sub> mL of C<sub>0</sub> mol/L NaCl with V mL AgNO<sub>3</sub> [<xref ref-type="bibr" rid="scirp.44200-ref5">5</xref>] . Denoting [Ag<sup>+</sup>][Cl<sup>–</sup>] = K<sub>so</sub> we get (13), where [<xref ref-type="bibr" rid="scirp.44200-ref5">5</xref>]</p><disp-formula id="scirp.44200-formula89323"><label>(14)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\0eab23cc-1ad5-44d7-88b8-790cdeada061.png"  xlink:type="simple"/></disp-formula><p>At pK<sub>so</sub> = 9.75 for AgCl, V<sub>0</sub> = 100 mL, C<sub>0</sub> = 10<sup>–4</sup> and C = 10<sup>–3</sup>, we get V<sub>eq</sub> – V<sub>inf</sub> = 0.16 mL.</p></sec><sec id="s3"><title>3. A Comment to Szyszkowski Formula</title><p>Many physicochemical processes are graphi&#173;cally represented by the curves with the sigmoidal shape. In this section, we refer to the function s = s(pH) obtained on the basis of Szyszkowski’s em&#173;pirical formula [<xref ref-type="bibr" rid="scirp.44200-ref6">6</xref>]</p><disp-formula id="scirp.44200-formula89324"><label>(15)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\bdfce44b-71ca-4913-829b-b0ef7a0b8785.png"  xlink:type="simple"/></disp-formula><p>expressing the relationship between surface tension s and concentration [HL] of uncharged form HL of an aliphatic fatty acid as a surfactant in aqueous media; s<sub>0</sub>—surface tension of pure water, a, b—constants.</p><p>Denoting <inline-formula><inline-graphic xlink:href="tmlimages\4-1000127x\0609c6b5-dde3-4c78-b179-a66a5492a42e.png" xlink:type="simple"/></inline-formula> and</p><p><img src="htmlimages\4-1000127x\8e527366-042b-4238-9645-a492665fde9c.png" /></p><p>we get, by turns:</p><p><img src="htmlimages\4-1000127x\ad452f69-fcd7-473d-83f6-cc767c33844f.png" /></p><p><img src="htmlimages\4-1000127x\525b0abc-838a-4404-93d7-ad1847a40707.png" /></p><p><img src="htmlimages\4-1000127x\6c9e0f19-b586-4cb6-8b65-f0ea3c8bc0d5.png" /><img src="htmlimages\4-1000127x\2a94375f-54c3-4fbf-8676-e748390f370c.png" /></p><p><img src="htmlimages\4-1000127x\f5aabbf6-a064-4330-be38-3d8faa879620.png" /></p><disp-formula id="scirp.44200-formula89325"><label>(16)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\c3272327-9fe7-447f-9c69-919d439ea35a.png"  xlink:type="simple"/></disp-formula><p>Putting d<sup>2</sup>s/dpH<sup>2</sup> = 0, from Equation (16) we get [H<sup>+</sup>]∙(1 + b∙C)<sup>1/2</sup> = K<sub>1</sub>, and then</p><disp-formula id="scirp.44200-formula89326"><label>(17)</label><graphic position="anchor" xlink:href="htmlimages\4-1000127x\89a138e0-e7f4-41b6-8d62-974813284b09.png"  xlink:type="simple"/></disp-formula><p>From Equation (17) it results that the abscissa (pH<sub>inf</sub>) corresponding to inflection point does not overlap with pK<sub>1</sub> value for HL.</p></sec></body><back><ref-list><title>References</title><ref id="scirp.44200-ref1"><label>1</label><mixed-citation publication-type="other" xlink:type="simple">Sigmoid Function. http://en.wikipedia.org/wiki/Sigmoid_function</mixed-citation></ref><ref id="scirp.44200-ref2"><label>2</label><mixed-citation publication-type="other" xlink:type="simple">Greschonig, H. and Glatter, O. (1986) Determination of Equivalence Points of Sigmoidal Potentiometric Titration Curves. Microchimica Acta, 89, 401-409. http://link.springer.com/article/10.1007%2FBF01207332</mixed-citation></ref><ref id="scirp.44200-ref3"><label>3</label><mixed-citation publication-type="journal" xlink:type="simple"><name name-style="western"><surname>Asuero</surname><given-names> A.G. and Michaowski</given-names></name>,<name name-style="western"><surname> T. </surname><given-names>  </given-names></name>,<etal>et al</etal>. (<year>2011</year>)<article-title>Comprehensive Formulation of Titration Curves for Complex Acid-Base Systems and Its Analytical Implications</article-title><source> Critical Reviews in Analytical Chemistry</source><volume> 41</volume>,<fpage> 151</fpage>-<lpage>187</lpage>.<pub-id pub-id-type="doi"></pub-id></mixed-citation></ref><ref id="scirp.44200-ref4"><label>4</label><mixed-citation publication-type="journal" xlink:type="simple"><name name-style="western"><surname>Michalowski</surname><given-names> T. </given-names></name>,<etal>et al</etal>. (<year>1981</year>)<article-title>Some Remarks on Acid-Base Titration Curves</article-title><source> Chemia Analityczna</source><volume> 26</volume>,<fpage> 799</fpage>-<lpage>813</lpage>.<pub-id pub-id-type="doi"></pub-id></mixed-citation></ref><ref id="scirp.44200-ref5"><label>5</label><mixed-citation publication-type="other" xlink:type="simple">Michalowski, T. and Stepak, R. (1985) Evaluation of the Equivalence Point in Potentiometric Titrations with Application to Traces of Chloride. Analytica Chimica Acta, 172, 207-214. http://dx.doi.org/10.1016/S0003-2670(00)82608-2</mixed-citation></ref><ref id="scirp.44200-ref6"><label>6</label><mixed-citation publication-type="other" xlink:type="simple">von Szyszkowski, B. (1908) Experimentelle Studien über kapillare Eigenschaften der wasserigen Losungen von Fettsauren. (Experimental studies of the capillary properties of aqueous solutions of fatty acids), Zeitschrift für Physikalische Chemie, 64, 385-414.</mixed-citation></ref></ref-list></back></article>