{"id":6079,"date":"2020-10-13T14:14:40","date_gmt":"2020-10-13T08:44:40","guid":{"rendered":"http:\/\/astan.lk\/al_virtualclassroom\/?p=6079"},"modified":"2020-10-13T14:14:20","modified_gmt":"2020-10-13T08:44:20","slug":"binary-component-system","status":"publish","type":"post","link":"https:\/\/astan.lk\/al_virtualclassroom\/binary-component-system\/","title":{"rendered":"Binary component system"},"content":{"rendered":"<p>\u2022 Liquid-liquid systems can be classified as<br \/>\n&#8211; Totally miscible liquid-liquid systems<br \/>\ne.g. water and ethanol, hexane and heptane, benzene and toluene.<br \/>\n&#8211; Partially miscible liquid-liquid systems<br \/>\ne.g. water and butanol, water and ether<br \/>\n&#8211; Totally immiscible liquid-liquid systems<br \/>\ne.g. water and tetrachloromethane<\/p>\n<h4><\/h4>\n<h4>Ideal liquid systems<\/h4>\n<p>In the case of a binary solution composed of totally miscible liquid components A and B, it may be possible that f<sub>(A-B)<\/sub> = f<sub>(A-A)<\/sub> = f<sub>(B-B)<\/sub> where f denotes inter-molecular attractive forces or interactions. Such a solution is called an ideal solution. When the components of an ideal solution are mixed (a) the volume does not change and (b) the enthalpy does not change (and hence there is no observable change in temperature).<\/p>\n<p>\u2022 When an ideal solution of A and B evaporates into a vacuum in a closed space, the molecules of both A and B with sufficient kinetic energy to surmount the liquid phase interactions escape from the surface into space above. At the same time, the molecules of A and B in motion in the vapour phase return to the liquid phase. When the rates of these two processes are equal, a dynamic equilibrium sets in. This is testified by the consistency of (a) the total vapour pressure (to which partial pressures of A and B contribute) and (b) the composition of the vapour phase at a constant temperature.<\/p>\n<p>\u2022 The composition of the vapour depends on (a) the relative volatilities of A and B (and hence their boiling points) and (b) the relative concentrations of A and B in the solution.<\/p>\n<p>\u2022 The higher the volatility and the higher the concentration of a certain component the greater is its tendency to be in the vapour phase and to exert a higher partial pressure.<\/p>\n<p>&nbsp;<\/p>\n<h4>Roults&#8217; law<\/h4>\n<p>\u2022 In order to find the composition of the vapour of an ideal binary solution quantitatively, let us consider the equilibria existing in a liquid-vapour system.<\/p>\n<p>A(l) \u00a0<b><span id=\"MathJax-Element-2-Frame\" class=\"MathJax\" style=\"display: inline; font-style: normal; font-weight: normal; line-height: normal; font-size: 13px; text-indent: 0px; text-align: left; text-transform: none; letter-spacing: normal; word-spacing: normal; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; position: relative;\" tabindex=\"0\" data-mathml=\"&lt;math xmlns=&quot;http:\/\/www.w3.org\/1998\/Math\/MathML&quot;&gt;&lt;mo class=&quot;MJX-variant&quot; stretchy=&quot;false&quot;&gt;&amp;#x21CC;&lt;\/mo&gt;&lt;\/math&gt;\"><span id=\"MathJax-Span-4\" class=\"math\"><span id=\"MathJax-Span-5\" class=\"mrow\"><span id=\"MathJax-Span-6\" class=\"mo\">\u21cc \u00a0<\/span><\/span><\/span><\/span><\/b>A(g)\u00a0&#8212;&#8212;-(1)<\/p>\n<p>B(l) \u00a0<b><span id=\"MathJax-Element-2-Frame\" class=\"MathJax\" style=\"display: inline; font-style: normal; font-weight: normal; line-height: normal; font-size: 13px; text-indent: 0px; text-align: left; text-transform: none; letter-spacing: normal; word-spacing: normal; word-wrap: normal; white-space: nowrap; float: none; direction: ltr; max-width: none; max-height: none; min-width: 0px; min-height: 0px; border: 0px; padding: 0px; margin: 0px; position: relative;\" tabindex=\"0\" data-mathml=\"&lt;math xmlns=&quot;http:\/\/www.w3.org\/1998\/Math\/MathML&quot;&gt;&lt;mo class=&quot;MJX-variant&quot; stretchy=&quot;false&quot;&gt;&amp;#x21CC;&lt;\/mo&gt;&lt;\/math&gt;\"><span id=\"MathJax-Span-4\" class=\"math\"><span id=\"MathJax-Span-5\" class=\"mrow\"><span id=\"MathJax-Span-6\" class=\"mo\">\u21cc \u00a0<\/span><\/span><\/span><\/span><\/b>B(g)\u00a0&#8212;&#8212;-(2)<\/p>\n<p>If R<sub>1<\/sub> is the rate of moving A from liquid phase to gas phase<br \/>\nR<sub>1<\/sub>= k\/ [A(l)]<br \/>\nSince [A(l)] is proportional to its mole fraction x<sub>A<\/sub> in the liquid phase,<br \/>\nR<sub>1<\/sub>= k<sub>1<\/sub> \u00d7 x<sub>A<\/sub> &#8212;&#8212;-(3)<br \/>\nIf R<sub>2<\/sub> is the rate of moving A from gas phase to liquid phase<br \/>\nR<sub>2<\/sub>= k&#8221; [A(g)]<br \/>\nSince [A(g)], is proportional to its partial pressure P<sub>A<\/sub><br \/>\nR<sub>2<\/sub>= k<sub>2<\/sub> \u00d7 P<sub>A<\/sub> &#8212;&#8212;&#8212;(4)<br \/>\nAt equilibrium R<sub>1<\/sub>= R<sub>2<\/sub><br \/>\nAccording to (3) and (4)<\/p>\n<p>k<sub>2<\/sub>P<sub>A<\/sub> = k<sub>1<\/sub>x<sub>A<\/sub><\/p>\n<p>\u2234P<sub>A<\/sub> = (k<sub>1<\/sub>\/k<sub>2<\/sub>)x<sub>A<\/sub><\/p>\n<p>\u2234P<sub>A<\/sub> = k x<sub>A<\/sub><\/p>\n<p>When x<sub>A<\/sub> = 1, P<sub>A<\/sub> = P<sup>0<\/sup><sub>A<\/sub><\/p>\n<p>k = P<sup>0<\/sup><sub>A<\/sub><br \/>\nP<sub>A<\/sub>= P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub><\/p>\n<p>\u2234Similarly P<sub>B<\/sub>= P<sup>0<\/sup><sub>B<\/sub><\/p>\n<p>Thus, in an ideal solution, the partial pressure of a given component A is equal to the product of the vapour pressure of pure A and the mole fraction of A in the liquid phase at constant temperature. This relationship is called Raoult&#8217;s law.<\/p>\n<p>\u2022 It is understood that P<sub>A<\/sub> &lt; P<sup>0<\/sup><sub>A<\/sub><br \/>\nand P<sub>B<\/sub> &lt; P<sup>0<\/sup><sub>B<\/sub><\/p>\n<p>Hence lowering in the vapour pressure of A = P<sup>0<\/sup><sub>A<\/sub>&#8211; P<sub>A<\/sub> \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0 \u00a0= P<sup>0<\/sup><sub>A &#8211;\u00a0<\/sub>P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub>\u00a0=P<sup>0<\/sup><sub>A <\/sub> (1 &#8211; x<sub>A<\/sub>\u00a0) =P<sup>0<\/sup><sub>A<\/sub>. x<sub>B<\/sub><\/p>\n<p>\u2234\u00a0\u00a0( P<sup>0<\/sup><sub>A<\/sub>&#8211; P<sub>A<\/sub> \u00a0 )\/ P<sup>0<\/sup><sub>A<\/sub>\u00a0 \u00a0= \u00a0x<sub>B<\/sub><\/p>\n<p>This is an alternate form of Raoults&#8217; law.<\/p>\n<p>&nbsp;<\/p>\n<p>\u2022 Combining Raoults&#8217; law with Dalton&#8217;s law of partial pressures, makes it possible to determine the composition of the vapour phase. If P<sub>AB<\/sub>\u00a0is the total vapour pressure and \u00a0y<sub>A<\/sub>\u00a0\u00a0and \u00a0y<sub>B<\/sub>\u00a0 are the mole fractions of A and B in the vapour phase respectively :<br \/>\nP<sub>A<\/sub>\u00a0=\u00a0P<sub>A<\/sub>\u00a0y<sub>A<\/sub><br \/>\n\u2234P<sub>A<\/sub>\u00a0 = (P<sub>A<\/sub>\u00a0 + P<sub>B<\/sub>\u00a0)\u00a0y<sub>A<\/sub><br \/>\n\u2234P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub> = (P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub> + P<sup>0<\/sup><sub>B<\/sub>. x<sub>B<\/sub>)\u00a0\u00a0y<sub>A<\/sub><\/p>\n<p><a href=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/rl.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-10207\" src=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/rl.png\" alt=\"\" width=\"239\" height=\"148\" \/><\/a><\/p>\n<p>\u2022 According to Raoult&#8217;s law P<sub>A<\/sub>= P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub>\u00a0. Since P<sup>0<\/sup><sub>A<\/sub>\u00a0is a constant at constant temperature,the graph of the partial vapour pressure of a component against its<br \/>\nmole fraction in an ideal solution is a straight line.<br \/>\n\u2022 Assuming A is more volatile than B(i.e. P<sup>0<\/sup><sub>A<\/sub>\u00a0&gt; P<sup>0<\/sup><sub>B<\/sub>\u00a0and \u2234 Tb(A) &lt; Tb(B)\u00a0the plot of vapour pressures versus mole fractions of an ideal solution will be as follows.<br \/>\nHere P<sub>AB<\/sub> is total pressure and P<sub>A<\/sub>\u00a0and P<sub>B<\/sub>\u00a0are vapour pressure of A and B respectively<\/p>\n<p><a href=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/il.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-10210\" src=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/il-300x263.png\" alt=\"\" width=\"221\" height=\"194\" \/><\/a><\/p>\n<p>examples -Hexane and heptane, benzene and toluene, bromoethane and iodoethane, CCl<sub>4<\/sub> and CHCl<sub>3<\/sub>,C<sub>6<\/sub>H<sub>6<\/sub> and C<sub>6<\/sub>D<sub>6<\/sub> (Note : P<sub>AB<\/sub> at a given composition is equal to P<sub>A<\/sub> + P<sub>B<\/sub>).<\/p>\n<p><a href=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/bpc.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-10213\" src=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/bpc-300x205.png\" alt=\"\" width=\"264\" height=\"180\" \/><\/a><\/p>\n<p>The boiling boint-composition graph, however, is not a straight line.<\/p>\n<p>&nbsp;<\/p>\n<h3>Non ideal systems<\/h3>\n<p>\u2022 Ideal solutions obey Raoults law. There are solutions which deviate from Raoult&#8217;s law. In these f<sub>(A-B)<\/sub> \u2260\u00a0f<sub>(A-A)<\/sub> \u2260\u00a0f<sub>(B-B)<\/sub>. These are non ideal solutions.<\/p>\n<p>&nbsp;<\/p>\n<h3>Negative deviate solution<\/h3>\n<p>\u2022 In some f<sub>(A-B)<\/sub> &gt;f<sub>(A-A)<\/sub> , f<sub>(A-B)<\/sub> &gt;f<sub>(B-B)<\/sub> \u00a0and and the freedom for molecules to escape into the vapour phase is lesser than in the case of an ideal solution.<\/p>\n<p>P<sub>A<\/sub><span style=\"font-size: 13.3333px;\">&lt;<\/span>\u00a0P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub><\/p>\n<p>P<sub>B<\/sub>&lt;\u00a0P<sup>0<\/sup><sub>B<\/sub>. x<sub>B<\/sub><\/p>\n<p>P<sub>AB<\/sub>\u00a0&lt; ( P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub>\u00a0+ \u00a0P<sup>0<\/sup><sub>B<\/sub>. x<sub>B<\/sub>\u00a0)<\/p>\n<p>Therefore, the curves in the vapour pressure &#8211; composition diagram dips downwards whereas the boiling point &#8211; composition curve rises up.<\/p>\n<p>e.g. Propanone and methanol, trichloromethane and propanone, ethanoic acid and water.<\/p>\n<p>These solutions are said to exhibit a negative deviation. When components of such solutions are mixed, temperature increases and volume decreases.<\/p>\n<p><a href=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/nds.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-10219\" src=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/nds-300x242.png\" alt=\"\" width=\"270\" height=\"218\" \/><\/a><\/p>\n<p>&nbsp;<\/p>\n<h3>Positive deviate solution<\/h3>\n<p>In some others \u00a0f<sub>(A-B)<\/sub>\u00a0&lt; f<sub>(A-A)<\/sub> , f<sub>(A-B)<\/sub>\u00a0&lt; f<sub>(B-B)<\/sub> and the molecules tend to escape more freely into the vapour phase than in the case of an ideal solution<\/p>\n<p>&nbsp;<\/p>\n<p>P<sub>A<\/sub><span style=\"font-size: 13.3333px;\">&gt;<\/span>\u00a0P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub><\/p>\n<p>P<sub>B<\/sub>&gt; P<sup>0<\/sup><sub>B<\/sub>. x<sub>B<\/sub><\/p>\n<p>P<sub>AB<\/sub>\u00a0&gt; ( P<sup>0<\/sup><sub>A<\/sub>. x<sub>A<\/sub>\u00a0+ \u00a0P<sup>0<\/sup><sub>B<\/sub>. x<sub>B<\/sub>\u00a0)<\/p>\n<p>Thus the curves in the vapour pressure &#8211; composition diagram loops upwards. The boiling point curve dips downwards.<br \/>\ne.g. Propanone and carbon disulphide, ethanol and benzene.<\/p>\n<p>These solutions show positive deviations from Raoult&#8217;s law.<br \/>\nWhen solvents of such solutions are mixed, temperature decreases and volume increases.<\/p>\n<p><a href=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/pds.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter wp-image-10218\" src=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/pds-292x300.png\" alt=\"\" width=\"188\" height=\"193\" \/><\/a><\/p>\n<p>&nbsp;<\/p>\n<p><a href=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/pds1.png\"><img loading=\"lazy\" decoding=\"async\" class=\"aligncenter size-medium wp-image-10217\" src=\"http:\/\/astan.lk\/al_virtualclassroom\/wp-content\/uploads\/2017\/01\/pds1-300x243.png\" alt=\"\" width=\"300\" height=\"243\" \/><\/a><\/p>\n<p>&nbsp;<\/p>\n<h4>Simple distillation<\/h4>\n<p>\u2022 Simple distillation can be used to get pure water from a solution of salt in water.<\/p>\n<p>\u2022 In addition to a distillation flask, for distillation a condenser is also need<\/p>\n<p>\u2022 In simple distillation only one component enters the vapour phase.<\/p>\n<p>&nbsp;<\/p>\n<h4>Fractional distillation<\/h4>\n<p><b>Using the phase diagram<\/b><\/p>\n<p>.\u00a0<img loading=\"lazy\" decoding=\"async\" src=\"http:\/\/www.chemguide.co.uk\/physical\/phaseeqia\/bpcompi7.gif\" width=\"397\" height=\"251\" \/><\/p>\n<pre><\/pre>\n<p>If you boil a liquid mixture C<sub>1<\/sub>, you will get a vapour with composition C<sub>2<\/sub>, which you can condense to give a liquid of that same composition (the pale blue lines).<\/p>\n<p>If you reboil that liquid C<sub>2<\/sub>, it will give a vapour with composition C<sub>3<\/sub>. Again you can condense that to give a liquid of the same new composition (the red lines).<\/p>\n<p>Reboiling the liquid C<sub>3<\/sub> will give a vapour still richer in the more volatile component B (the green lines). You can see that if you were to do this once or twice more, you would be able to collect a liquid which was virtually pure B.<\/p>\n<p>The secret of getting the more volatile component from a mixture of liquids is obviously to do a succession of boiling-condensing-reboiling operations.<\/p>\n<p>&nbsp;<\/p>\n<p>&nbsp;<\/p>\n<p><b>The apparatus<\/b><\/p>\n<p>A typical lab fractional distillation would look like this:<\/p>\n<pre><\/pre>\n<p align=\"center\"><img loading=\"lazy\" decoding=\"async\" class=\"\" src=\"http:\/\/www.chemguide.co.uk\/physical\/phaseeqia\/apparatus.gif\" width=\"366\" height=\"427\" \/><\/p>\n<pre><\/pre>\n<p>The fractionating column is packed with glass beads (or something similar) to give the maximum possible surface area for vapour to condense on. \u00a0Some fractionating columns have spikes of glass sticking out from the sides which serve the same purpose.<\/p>\n<p>The mixture is heated at such a rate that the thermometer is at the temperature of the boiling point of the more volatile component. Notice that the thermometer bulb is placed exactly at the outlet from the fractionating column.<\/p>\n<p><b>Relating what happens in the fractionating column to the phase diagram<\/b><\/p>\n<p>Suppose you boil a mixture with composition C<sub>1<\/sub>.<\/p>\n<p>The vapour over the top of the boiling liquid will be richer in the more volatile component, and will have the composition C<sub>2<\/sub>.<\/p>\n<pre><\/pre>\n<p align=\"center\"><img loading=\"lazy\" decoding=\"async\" src=\"http:\/\/www.chemguide.co.uk\/physical\/phaseeqia\/bpcompi8.gif\" width=\"397\" height=\"254\" \/><\/p>\n<pre><\/pre>\n<p>That vapour now starts to travel up the fractionating column. Eventually it will reach a height in the column where the temperature is low enough that it will condense to give a liquid. The composition of that liquid will, of course, still be C<sub>2<\/sub>.<\/p>\n<p>&nbsp;<\/p>\n<pre><\/pre>\n<p align=\"center\"><img loading=\"lazy\" decoding=\"async\" src=\"http:\/\/www.chemguide.co.uk\/physical\/phaseeqia\/bpcompi9.gif\" width=\"396\" height=\"251\" \/><\/p>\n<pre><\/pre>\n<p>Some of the liquid of composition C<sub>2<\/sub> will boil to give a vapour of composition C<sub>3<\/sub>. Let&#8217;s concentrate first on that new vapour and think about the unvaporised part of the liquid afterwards.<\/p>\n<p><b><i>The vapour<\/i><\/b><\/p>\n<p>This new vapour will again move further up the fractionating column until it gets to a temperature where it can condense. Then the whole process repeats itself.<\/p>\n<p>Each time the vapour condenses to a liquid, this liquid will start to trickle back down the column where it will be reboiled by up-coming hot vapour. Each time this happens the new vapour will be richer in the more volatile component.<\/p>\n<p>The aim is to balance the temperature of the column so that by the time vapour reaches the top after huge numbers of condensing and reboiling operations, it consists only of the more volatile component &#8211; in this case, B.<\/p>\n<p>Whether or not this is possible depends on the difference between the boiling points of the two liquids. The closer they are together, the longer the column has to be.<\/p>\n<p><b><i>The liquid<\/i><\/b><\/p>\n<p>So what about the liquid left behind at each reboiling? Obviously, if the vapour is richer in the more volatile component, the liquid left behind must be getting richer in the other one.<\/p>\n<p>As the condensed liquid trickles down the column constantly being reboiled by up-coming vapour, each reboiling makes it richer and richer in the less volatile component &#8211; in this case, A. By the time the liquid drips back into the flask, it will be very rich in A indeed.<\/p>\n<p>So, over time, as B passes out of the top of the column into the condenser, the liquid in the flask will become richer in A. If you are very, very careful over temperature control, eventually you will have separated the mixture into B in the collecting flask and A in the original flask.<\/p>\n","protected":false},"excerpt":{"rendered":"<p>\u2022 Liquid-liquid systems can be classified as &#8211; Totally miscible liquid-liquid systems e.g. water and ethanol, hexane and heptane, benzene and toluene. &#8211; Partially miscible liquid-liquid systems e.g. water and butanol, water and ether &#8211; Totally immiscible liquid-liquid systems e.g. water and tetrachloromethane Ideal liquid systems In the case of a binary solution composed of [&hellip;]<\/p>\n","protected":false},"author":842,"featured_media":0,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"_monsterinsights_skip_tracking":false,"_monsterinsights_sitenote_active":false,"_monsterinsights_sitenote_note":"","_monsterinsights_sitenote_category":0,"footnotes":""},"categories":[14,1676],"tags":[],"class_list":["post-6079","post","type-post","status-publish","format-standard","hentry","category-chemistry","category-unit-13"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v26.9 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>Binary component system - Learning &amp; 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