{"id":10150,"date":"2016-09-16T08:03:13","date_gmt":"2016-09-16T12:03:13","guid":{"rendered":"https:\/\/www.masterorganicchemistry.com\/?p=10150"},"modified":"2025-09-24T10:39:03","modified_gmt":"2025-09-24T15:39:03","slug":"introduction-to-uv-vis-spectroscopy","status":"publish","type":"post","link":"https:\/\/www.masterorganicchemistry.com\/2016\/09\/16\/introduction-to-uv-vis-spectroscopy\/","title":{"rendered":"Introduction To UV-Vis Spectroscopy"},"content":{"rendered":"<p><strong>Understanding UV-Vis Spectroscopy Will Make You More Fun At Parties<\/strong><\/p>\n<p>In today&#8217;s post we&#8217;ll discuss why most molecules are colourless, introduce the useful technique of UV-visible spectroscopy, and finally explain\u00a0<em>why<\/em> molecules like chlorophyll and \u03b2-carotene are coloured.<\/p>\n<p>We&#8217;ll even finish by showing you how to use a UV-Vis spectrum to predict the color of a molecule, which is a great trick to roll out at parties. No, seriously, it&#8217;s incredible. We&#8217;re talking about understanding the chemistry of colour, everyone! It doesn&#8217;t get better than this.<\/p>\n<p>First,\u00a0the summary. We&#8217;ll walk through the\u00a0details below.<\/p>\n<p><img fetchpriority=\"high\" decoding=\"async\" class=\"alignnone wp-image-15443\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/0-summary-of-uv-vis-spectroscopy-uv-light-excites-electron-from-lumo-to-homo-.gif\" alt=\"summary of uv vis spectroscopy uv light excites electron from lumo to homo\" width=\"600\" height=\"977\" \/><\/p>\n<p><strong>Table of Contents<\/strong><\/p>\n<ol>\n<li><a href=\"#one\">Converting Frequency Units Into Energy\u00a0 Units<\/a><\/li>\n<li><a href=\"#two\">Ground\u00a0 State Electrons Can Be Promoted To Excited\u00a0 States Through The Absorption\u00a0 Of Light<\/a><\/li>\n<li><a href=\"#three\">Case Study: The Molecular Orbital\u00a0 Diagram Of H2<\/a><\/li>\n<li><a href=\"#four\">Why Most Molecules Containing Only Single Bonds Are\u00a0 Colorless<\/a><\/li>\n<li><a href=\"#five\">Pi Bonds Absorb At Longer, More Energetically Accessible Wavelengths<\/a><\/li>\n<li><a href=\"#six\">The UV-Vis Spectrometer<\/a><\/li>\n<li><a href=\"#seven\">How Does\u00a0 Conjugation Of Pi Bonds Affect Lambda Max?<\/a><\/li>\n<li><a href=\"#eight\">How Does Lambda Max Relate To The Color We Perceive?<\/a><\/li>\n<li><a href=\"#nine\">Conclusion: UV-Vis Spectroscopy<\/a><\/li>\n<li><a href=\"#notes\">Notes<\/a><\/li>\n<li><a href=\"#quizzes\">Quiz Yourself!<\/a><\/li>\n<\/ol>\n<hr \/>\n<h2><strong><a id=\"one\"><\/a>1. Converting The Frequency Of Light Into Energy Units<\/strong><\/h2>\n<p>If you want someone to read something you&#8217;ve wrote, starting with an equation is generally a bad idea. However, we&#8217;re going to start with one of the most beautiful, amazing, and just plain\u00a0<em>useful\u00a0<\/em>equations in all of science. So if you drop off after reading this, really, that&#8217;s your problem.<\/p>\n<p>From general chemistry, you may recall the immortal equation<\/p>\n<p>E = <em>h\u03bd <\/em><\/p>\n<p>where <strong>E<\/strong> is energy, <strong><em>h<\/em><\/strong> is Planck&#8217;s constant (6.626 \u00d7 10<sup>-34<\/sup>\u00a0m<sup>2<\/sup>\u00a0kg \/ s\u00a0) and\u00a0<em><strong>\u03bd<\/strong>\u00a0<\/em>is frequency \u00a0(in m<sup>-1<\/sup>) .<\/p>\n<p>Why is this equation so frickin&#8217; useful? <strong>Because it\u00a0relates energy to the frequency of light.\u00a0<\/strong><\/p>\n<p>To be more specific, when I say &#8220;light&#8221; I mean, &#8220;photon&#8221;, as in a carrier of electromagnetic radiation. For the purposes of today&#8217;s post, here&#8217;s the part of the <a href=\"https:\/\/en.wikipedia.org\/wiki\/Electromagnetic_spectrum\">electromagnetic spectrum<\/a> we&#8217;ll be discussing today: the UV and visible frequencies.<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15434\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/1-electromagnetic-spectrum-for-spectroscopy-organic-chemistry-applications-e-equals-hv-uv-and-visible.gif\" alt=\"electromagnetic spectrum for spectroscopy organic chemistry applications e equals hv uv and visible\" width=\"630\" height=\"220\" \/><\/p>\n<h2><a id=\"two\"><\/a>2. Ground State Electrons Can Be Promoted To Excited States Through The Absorption of Light<\/h2>\n<p>Way back in general chemistry (<a href=\"https:\/\/en.wikipedia.org\/wiki\/Bohr_model\">Bohr model of the hydrogen atom<\/a>, anyone?) you saw how an electron can be promoted from the<strong> ground state<\/strong> orbital to an <strong>excited-state<\/strong> orbital through the absorption of a photon of frequency:<\/p>\n<p>\u03bd\u00a0=\u00a0\u0394E \/\u00a0<em>h <\/em><\/p>\n<p><em>\u00a0<\/em>[where\u00a0\u0394E is the difference in energy between the ground and excited states].<\/p>\n<p>Since it is an electron that is being promoted from one energy level to another, we call these &#8220;<strong>electronic transitions<\/strong>&#8220;. Generally, the frequency of radiation required for electronic transitions is in the\u00a0<strong>ultraviolet and visible portion\u00a0<\/strong>of the electromagnetic spectrum.<\/p>\n<p>This has practical importance in a great number of ways, but for our purposes, we&#8217;ll see that the most prominent is that light can promote electrons from\u00a0<strong>bonding<\/strong> orbitals to\u00a0<strong>anti bonding\u00a0<\/strong>orbitals, and therefore potentially lead to the breaking of chemical bonds.<\/p>\n<p>This\u00a0will help\u00a0us to understand:<\/p>\n<ul>\n<li>why molecules absorb UV light in the first place (sigma -&gt; sigma* transitions)<\/li>\n<li>why UV radiation is extremely harmful (especially far-UV radiation)<\/li>\n<li>and ultimately, why certain molecules have color (pi &#8211;&gt; pi* transitions)<\/li>\n<\/ul>\n<p>Let&#8217;s start with the simplest molecule, hydrogen (H<sub>2<\/sub>) and build from there.<\/p>\n<h2><a id=\"three\"><\/a>3. Case Study: The Molecular Orbital Diagram For of Molecular Hydrogen (H<sub>2<\/sub>)<\/h2>\n<p>In the beginning of your organic chemistry course, you likely saw how atomic orbitals can overlap to form\u00a0<strong>molecular<\/strong> orbitals.<\/p>\n<p>In hydrogen (H<sub>2<\/sub>), for example, two <strong>1s<\/strong> <strong>atomic<\/strong> <strong>orbitals<\/strong> overlap to form two sigma ( \u03c3) <strong>molecular orbitals<\/strong>. The number of orbitals is always conserved: since we start with two atomic orbitals, we end up with two molecular orbitals.<\/p>\n<p><strong>Constructive<\/strong> overlap leads to the formation of the lower-energy sigma ( \u03c3 )orbital. <strong>Destructive<\/strong> overlap leads to the formation of the higher energy sigma star (\u03c3*) orbital. These two orbitals differ by energy\u00a0<strong>\u0394E<\/strong> .<\/p>\n<p>Since each\u00a0hydrogen atom brings one electron to the party, we have two electrons to fill up our molecular orbitals with, and they will fill up the lower energy orbitals first &#8211; much like how nobody chooses to stand in the aisle of a city bus (higher energy) when an empty seat is present (lower energy).<\/p>\n<p>This gives us a diagram that looks like this: (If \u00a0you find this intimidating, just\u00a0focus on that red \u00a0<span style=\"color: #ff0000;\"><strong>\u0394E<\/strong><\/span>).<\/p>\n<p><img decoding=\"async\" class=\"alignnone wp-image-15435\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/2-simple-energy-diagram-for-dihydrogen-h2-showing-sigma-and-sigma-star-homo-and-lumo-with-delta-e-energy-gap.gif\" alt=\"simple energy diagram for dihydrogen h2 showing sigma and sigma star homo and lumo with delta e energy gap\" width=\"600\" height=\"520\" \/><\/p>\n<p>That\u00a0<strong><span style=\"color: #ff0000;\">\u0394E<\/span>\u00a0<\/strong>is important: by\u00a0analogy to the\u00a0Bohr model, if molecular hydrogen (H<sub>2<\/sub>) is exposed to light\u00a0of frequency<\/p>\n<p>\u03bd\u00a0=\u00a0\u0394E \/\u00a0<em>h\u00a0<\/em><\/p>\n<p>an electron will be promoted from the ground state (sigma) molecular orbital (the <strong>highest occupied molecular orbital<\/strong>, or <strong>HOMO)<\/strong> \u00a0to the excited sigma* molecular orbital (the <strong>lowest unoccupied molecular orbital<\/strong> or <strong>LUMO<\/strong>).<\/p>\n<p>It&#8217;s a bit like how toddlers climb stairs, one step at a time:\u00a0\u00a0one foot\u00a0ascends\u00a0from the <strong>highest occupied step<\/strong> to the <strong>lowest unoccupied step<\/strong>, and the energy necessary to do this is determined by the difference in height between the steps.<\/p>\n<p>Now, we can convert frequency to wavelength through the equation<\/p>\n<p>c =\u00a0\u03bd\u00a0\u03bb \u00a0 (c is the speed of light,\u00a0\u03bb is wavelength).<\/p>\n<p>For the H-H bond in H<sub>2<\/sub>, \u0394E\u00a0corresponds to a measured absorption wavelength maximum of <strong>112 nm<\/strong>, which is deep, deep, <em>deep<\/em> in the UV region of the electromagnetic spectrum.<\/p>\n<h2><a id=\"four\"><\/a>4. Why Most Molecules Containing Only Single Bonds Are Colourless<\/h2>\n<p>112 nm\u00a0is not exactly the tanning-bed\u00a0area of the UV. No, <strong>this is the death-ray part of the UV spectrum.\u00a0<\/strong>That&#8217;s because UV radiation below 120 nm is also where common sigma bonds like C-H and C-C absorb, and hence being exposed to far-UV light would quickly fragment the bonds that make up the proteins, sugars, and DNA present in our bodies and turn us to goo.<\/p>\n<p>Let&#8217;s make this more clear.<\/p>\n<p><strong>Most single (i.e. sigma) bonds such as C-C, C-H, O-H, and C-O \u00a0have\u00a0\u0394E values that correspond to light in the deep UV part of the spectrum.\u00a0<\/strong>They appear colourless to us because light in the visible region (400-700 nm) simply doesn&#8217;t have enough energy to excite their bonding electrons to an excited state.<\/p>\n<p>This is why water is colourless. This is why ethanol is colourless. This is why diethyl ether, hexanes, chloroform, and a host of other molecules you encounter both in the lab and in everyday life are colourless: <strong>the \u0394E for the bonding orbitals is too\u00a0large\u00a0<\/strong>for relatively low-energy photons of visible light to excite them. <del>[Insert Jeb Bush joke?]<\/del><\/p>\n<p>In fact, UV in the region below 120 nm is so energetic, it is completely absorbed by atmospheric O<sub>2<\/sub> and N<sub>2<\/sub>. In other words, if you want to measure the exact wavelengths that , say, ethanol\u00a0absorbs at, you would need to place it in a vacuum chamber and expose it to hard UV light. \u00a0This is of academic interest, sure, but outside the scope of a typical intro course. For our purposes, we won&#8217;t discuss\u00a0sigma \u2192 sigma* transitions further.<\/p>\n<p><strong>Bottom line:<\/strong>\u00a0we don&#8217;t generally observe sigma \u2192 sigma* transitions.<\/p>\n<p><span style=\"color: #993366;\"><em>[One exception that we do encounter are dihalogens like Cl<sub>2<\/sub> and I<sub>2<\/sub>\u00a0that can absorb visible light to <a style=\"color: #993366;\" href=\"https:\/\/www.masterorganicchemistry.com\/2013\/09\/06\/initiation-propagation-termination\/\">generate free radicals through homolytic cleavage of sigma bonds<\/a>\u00a0. This is an example of breaking sigma bonds through absorption of UV or visible light, made possible because these bonds are quite weak, about 50-60 kcal\/mol, and the corresponding \u0394E is small ].<\/em><\/span><\/p>\n<h2><a id=\"five\"><\/a>5. Pi ( \u03c0) bonds absorb at longer, more accessible wavelengths<\/h2>\n<p>OK: we&#8217;re going to ignore \u03c3\u2192\u03c3* transitions.\u00a0So let&#8217;s talk about \u03c0-\u03c0* transitions instead.<strong>\u00a0<\/strong><\/p>\n<p><strong><em>This is where it gets interesting and relevant.\u00a0<\/em><\/strong><\/p>\n<p>Let&#8217;s remind ourself of what we&#8217;re talking about by starting with a simple molecule.\u00a0Here&#8217;s ethene (a.k.a. &#8220;ethylene&#8221;), the simplest alkene. A quick look at its structure reveals <strong>5 sigma bonds<\/strong> and <strong>one pi bond<\/strong>.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15436\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/3-all-bonds-in-ethene-sigma-bond-framework-with-end-on-overlap-pi-bond-framework-with-side-on-overlap-5-sigma-bonds-1-pi-bond.gif\" alt=\"all bonds in ethene sigma bond framework with end on overlap pi bond framework with side on overlap 5 sigma bonds 1 pi bond\" width=\"600\" height=\"431\" \/><\/p>\n<ul>\n<li>Recall that sigma bonds are the result of <strong>&#8220;end-on&#8221;<\/strong> overlap between s \u00a0or sp<sup>n <\/sup>(sp, sp<sup>2<\/sup>, or sp<sup>3<\/sup>)\u00a0orbitals , whereas pi bonds result from the <strong>&#8220;side-on&#8221;<\/strong> bonding of adjacent p orbitals.<\/li>\n<\/ul>\n<ul>\n<li>All else being equal,\u00a0\u00a0\u03c0 bonds are <strong>weaker<\/strong> than the comparable sigma bonds, because there is less orbital overlap.<\/li>\n<\/ul>\n<ul>\n<li><strong>Weaker bonds<\/strong> mean that the energy gap\u00a0\u0394E between \u00a0the \u03c0 (HOMO) and \u03c0* (LUMO) will be correspondingly <strong>smaller<\/strong>. [In our analogy, a shorter step in a staircase requires less energy to climb].<\/li>\n<\/ul>\n<ul>\n<li>Since \u0394E is <strong>smaller<\/strong> for a pi bond, this corresponds to a\u00a0<strong><em>longer<\/em> wavelength<\/strong> (of<em> lower frequency<\/em>) required to excite an electron from the pi to the pi* orbital.<\/li>\n<\/ul>\n<p>For ethene, the wavelength absorption maximum for this pi-pi* transition is about 170 nm: <strong>still in the deep UV, but not as extreme as for the corresponding C-C sigma bond.<\/strong><\/p>\n<p>We&#8217;d expect ethylene to be colourless, and it is: \u00a0it just absorbs a\u00a0somewhat\u00a0closer to the visible portion of the spectrum than, say, ethane.<\/p>\n<p>Let&#8217;s illustrate this with\u00a0a figure\u00a0that often\u00a0looks scary to students: an orbital energy diagram.<\/p>\n<p>*Trigger Warning* All this figure is trying to show is that <span style=\"color: #ff0000;\"><strong>\u0394E<\/strong><\/span> for the C-C \u03c0 bond (<span style=\"color: #339966;\"><strong>in green<\/strong><\/span>) is smaller than <span style=\"color: #999999;\"><strong>\u0394E<\/strong><\/span> for the C-C \u03c3\u00a0bond (<span style=\"color: #808080;\"><strong>in grey)<\/strong><\/span>. If you get that, you&#8217;ve grasped the key point.*<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15437\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/4-partial-energy-diagram-for-ethene-showing-sigma-and-pi-bonding-showing-lumo-and-homo-gap-for-ethene-absorption-wavelength-170.gif\" alt=\"partial energy diagram for ethene showing sigma and pi bonding showing lumo and homo gap for ethene absorption wavelength 170\" width=\"600\" height=\"704\" \/><\/p>\n<p>Wait a second, you might say.\u00a0How do we\u00a0<em>know<\/em> that ethene absorbs light in the UV around 170 nm?<\/p>\n<p>Glad you asked. Let&#8217;s introduce a very important device\u00a0called a <strong>UV-Vis Spectrometer<\/strong>.<\/p>\n<h2><strong><a id=\"six\"><\/a>6. The UV-Vis Spectrometer<\/strong><\/h2>\n<p>The basic idea behind <a href=\"https:\/\/en.wikipedia.org\/wiki\/Ultraviolet\u2013visible_spectroscopy\">UV-Vis spectroscopy<\/a> is to shine light of varying wavelengths\u00a0through a sample and to <strong>measure the absorbance at each wavelength<\/strong>. Only the wavelengths corresponding to the\u00a0\u0394E for an electronic transition will be strongly absorbed. <span style=\"color: #993366;\"><em>[For a schematic of how the spectrometer works: check this <strong><a style=\"color: #993366;\" href=\"http:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry_Textbook_Maps\/Map%3A_Organic_Chemistry_With_a_Biological_Emphasis_(Soderberg)\/Chapter_04%3A_Structure_Determination_I\/4.3%3A_Ultraviolet_and_visible_spectroscopy\">excellent page<\/a><\/strong>, which is also an excellent alternative explanation of UV].<\/em><\/span><\/p>\n<p>A UV-Vis spectrum plots absorbance (or its inverse, transmittance) of the sample versus wavelength. \u00a0Here&#8217;s the spectrum for ethene. <span style=\"color: #993366;\"><em>[In this case the wavelength is plotted versus\u00a0transmittance, the inverse of absorbance (high absorbance = low transmittance, and vice versa). ]<\/em><\/span><\/p>\n<p>Note that the\u00a0<strong>wavelength of maximum transmittance\u00a0<\/strong>is at 174 nm. <strong>We call this \u00a0\u03bb<sub>max<\/sub>\u00a0,\u00a0<\/strong> pronounced &#8220;lambda max&#8221;. Very little light passes through the sample at this wavelength, because the wavelength corresponds very closely to\u00a0\u0394E for the \u03c0\u00a0to \u03c0* transition.\u00a0<a href=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2016\/09\/ethene-e1473960939339.png\"><br \/>\n<\/a><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15438\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition.png\" alt=\"uv vis spectrum of ethylene ethene with lambda max of 174 pi to pi star transition\" width=\"600\" height=\"450\" srcset=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition.png 800w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-300x225.png 300w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-768x576.png 768w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-320x240.png 320w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-640x480.png 640w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-360x270.png 360w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-720x540.png 720w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/5-uv-vis-spectrum-of-ethylene-ethene-with-lambda-max-of-174-pi-to-pi-star-transition-760x570.png 760w\" sizes=\"(max-width: 600px) 100vw, 600px\" \/><\/p>\n<p>The UV-Vis spectrometer is a useful tool because it allows us to nail down exactly where samples absorb light, and thus\u00a0<strong>quantify<\/strong> electronic transitions. For example, knowing that the \u00a0\u03bb<sub>max\u00a0<\/sub>for ethene is at 174 nm allows us to calculate the energy gap\u00a0\u0394E , which turns out to be about 164 kcal\/mol.<\/p>\n<h2><strong><a id=\"seven\"><\/a>7. How Does Conjugation Of Pi Bonds Affect\u00a0\u00a0\u03bb<sub>max<\/sub> ?<\/strong><\/h2>\n<p>In our <strong><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/09\/08\/how_bleach_works\/\">previous post on natural pigments,<\/a>\u00a0<\/strong>we\u00a0noted that their <strong>\u00a0large number of conjugated pi bonds\u00a0<\/strong>was responsible for their colors.<\/p>\n<p>UV-Vis spectroscopy helps us to understand\u00a0<strong>exactly how conjugation relates to the \u03bb<sub>max<\/sub>\u00a0of a molecule &#8211; and thus, its color\u00a0<\/strong>(or lack thereof).<\/p>\n<p>For example, let&#8217;s look at what happens to \u03bb<sub>max<\/sub>\u00a0when we increase the conjugation length from 1 (ethene) to 2 (butadiene) to 3 (hexatriene).<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15439\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/6-conjugation-increases-lambda-max-difference-between-ethene-butadiene-hexatriene-higher-lambda-max-for-triene-towards-visible.gif\" alt=\"conjugation increases lambda max difference between ethene butadiene hexatriene higher lambda max for triene towards visible\" width=\"600\" height=\"364\" \/><\/p>\n<p><strong>As the number of conjugated pi bonds increases, the\u00a0\u03bb<sub>max<\/sub> increases as well!\u00a0<\/strong><\/p>\n<p>Because longer frequency = smaller energy, this means that the <strong>energy gap\u00a0\u0394E<\/strong> between the highest-occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) <strong>decreases<\/strong> as the number of conjugated pi bonds <strong>increases.<\/strong><\/p>\n<p>For kicks, here&#8217;s what the bonding picture (roughly) looks like. Again, just focus on the\u00a0<span style=\"color: #ff0000;\"><strong>\u0394E<span style=\"color: #000000;\">:\u00a0<\/span><\/strong><span style=\"color: #000000;\">it gets smaller as the number of conjugated pi bonds increases.\u00a0<\/span><\/span><\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15440\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/7-simple-molecular-orbital-diagram-ethene-butadiene-hexatriene-showing-smaller-homo-lumo-gap-meaning-longer-absorbption-wavelength.gif\" alt=\"simple molecular orbital diagram ethene butadiene hexatriene showing smaller homo lumo gap meaning longer absorbption wavelength\" width=\"600\" height=\"431\" \/><\/p>\n<p>As this trend continues past hexatriene toward molecules with longer conjugation length,\u00a0\u03bb<sub>max\u00a0<\/sub>starts to creep into the visible region of the spectrum. It&#8217;s already at 258 nm for a conjugation length of 3. Color starts to appear when the conjugation length approaches 7 or so. \u00a0<span style=\"color: #993366;\"><em> [For instance, <a style=\"color: #993366;\" href=\"https:\/\/en.wikipedia.org\/wiki\/Amphotericin_B\">Amphotericin B<\/a> has 7 conjugated pi bonds\u00a0and absorbs around 403 nm, in the violet.]<\/em><\/span><\/p>\n<p>Our old friends <a href=\"https:\/\/en.wikipedia.org\/wiki\/Lycopene\">lycopene<\/a> (\u03bb<sub>max\u00a0<\/sub>471 nm),\u00a0<a href=\"https:\/\/en.wikipedia.org\/wiki\/Beta-Carotene\">\u03b2-carotene<\/a> (\u03bb<sub>max\u00a0<\/sub>452 nm) and <a href=\"https:\/\/en.wikipedia.org\/wiki\/Lutein\">lutein <\/a>(\u03bb<sub>max<\/sub> \u00a0445 nm) have even larger pi systems (10 and 11) and absorb visible light further towards the red. [<a href=\"#notetwo\">Note 2<\/a>]<\/p>\n<p>Thus,\u00a0<strong>the \u03bb<sub>max<\/sub> of molecules are largely a function of the conjugation length: as conjugation number increases, so does\u00a0\u03bb<sub>max<\/sub><sub>.\u00a0<\/sub><\/strong><\/p>\n<p>But one question remains:<\/p>\n<h2><a id=\"eight\"><\/a>8. How Does \u03bb<sub>max\u00a0<\/sub>Relate To The Color We Perceive?<\/h2>\n<p>One last piece of the puzzle. How does the wavelength of maximum absorbance (\u03bb<sub>max<\/sub>) relate to the actual\u00a0<strong>color?\u00a0<\/strong><\/p>\n<p><strong>First,<\/strong>\u00a0a refresher from the last post. We see the complementary colour of the major color that is absorbed.\u00a0<strong>\u00a0<\/strong>A molecule that absorbs in the <strong>blue<\/strong> will appear\u00a0<strong>orange<\/strong>, because we perceive the colors that are\u00a0<em>reflected<\/em>, and\u00a0<strong>orange<\/strong>\u00a0is the complementary color of blue.<\/p>\n<p>For example, this molecule, Rhodamine B [<a href=\"#notethree\">Note 3<\/a>] absorbs at about 560 nm (<strong>green<\/strong>) \u00a0and appears\u00a0<strong>red<\/strong>\u00a0, the complimentary color of green.<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15441\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-relationship-between-lambda-max-and-perceived-color-the-color-is-the-complimentary-color-of-wavelength-of-light-absorbed-green-absorption-means-red-color.png\" alt=\"relationship between lambda max and perceived color the color is the complimentary color of wavelength of light absorbed green absorption means red color\" width=\"450\" height=\"230\" srcset=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-relationship-between-lambda-max-and-perceived-color-the-color-is-the-complimentary-color-of-wavelength-of-light-absorbed-green-absorption-means-red-color.png 596w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-relationship-between-lambda-max-and-perceived-color-the-color-is-the-complimentary-color-of-wavelength-of-light-absorbed-green-absorption-means-red-color-300x154.png 300w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-relationship-between-lambda-max-and-perceived-color-the-color-is-the-complimentary-color-of-wavelength-of-light-absorbed-green-absorption-means-red-color-320x164.png 320w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/8-relationship-between-lambda-max-and-perceived-color-the-color-is-the-complimentary-color-of-wavelength-of-light-absorbed-green-absorption-means-red-color-360x184.png 360w\" sizes=\"(max-width: 450px) 100vw, 450px\" \/><\/p>\n<p>Knowing where a molecule absorbs visible light allows us to make predictions about its color.\u00a0Interesting!<\/p>\n<p>That is a pretty badass cocktail party trick, \u00a0I think. Think about that the next time you look at a leaf, a tomato, a carrot, or yellow crayfish blood.<\/p>\n<p>We could go on (and we will!) . But let&#8217;s leave it there for now.<\/p>\n<p>BTW: A fantastic treatment of UV-Vis spectroscopy with less jibber-jabber has been written by <a href=\"http:\/\/chem.libretexts.org\/Textbook_Maps\/Organic_Chemistry_Textbook_Maps\/Map%3A_Organic_Chemistry_With_a_Biological_Emphasis_(Soderberg)\/Chapter_04%3A_Structure_Determination_I\/4.3%3A_Ultraviolet_and_visible_spectroscopy\">Tim Soderbergh over at LibreText. Check it out<\/a>.<\/p>\n<p>Also, <a href=\"https:\/\/www2.chemistry.msu.edu\/faculty\/reusch\/virttxtjml\/spectrpy\/uv-vis\/spectrum.htm\">Reusch&#8217;s online textbook entry on UV-Vis spectroscopy<\/a> is more in-depth and richer in deep detail on this topic than this post is.<\/p>\n<h2><a id=\"nine\"><\/a>9. Conclusion: UV-Vis Spectroscopy<\/h2>\n<p>This post has\u00a0walked through some of the theory behind UV-Vis spectra.<\/p>\n<p>In the next post, we&#8217;ll go into some of the more practical aspects of UV-Vis spectroscopy. What kind of questions can UV-Vis help us answer about an unknown molecule?<\/p>\n<p>&nbsp;<\/p>\n<hr \/>\n<h2><a id=\"notes\"><\/a>Notes<\/h2>\n<div class=\"related-articles\"><p><strong>Related Articles<\/strong><\/p><ul><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/09\/08\/conjugation_and_color\/\" class=\"\"><span>Conjugation And Color (+ How Bleach Works)<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2017\/01\/24\/conjugation-and-resonance\/\" class=\"\"><span>Conjugation And Resonance In Organic Chemistry<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/09\/26\/uv-vis-spectroscopy-absorbance-of-carbonyls\/\" class=\"\"><span>UV-Vis Spectroscopy: Absorbance of Carbonyls<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/09\/27\/uv-vis-spectroscopy-some-practice-questions\/\" class=\"\"><span>UV-Vis Spectroscopy: Practice Questions<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/11\/29\/ir-spectroscopy-some-simple-practice-problems\/\" class=\"\"><span>IR Spectroscopy: 4 Practice Problems<\/span><\/a><\/li><li><a href=\"https:\/\/www.masterorganicchemistry.com\/2016\/11\/23\/quick_analysis_of_ir_spectra\/\" class=\"\"><span>Infrared Spectroscopy: A Quick Primer On Interpreting Spectra<\/span><\/a><\/li><\/ul><\/div>\n<p><a id=\"noteone\"><\/a><strong>Note 1<\/strong>.\u00a0 What&#8217;s missing from this discussion?<\/p>\n<p>The \u00a0\u03bb<sub>max<\/sub>isn&#8217;t <em>solely<\/em> a function of the number of pi bonds. If that were true, lycopene (11 conjugated pi bonds) and\u00a0b-carotene (also with 11 conjugated pi bonds) would have the exact same color. They don&#8217;t, since\u00a0\u00a0\u03bb<sub>max <\/sub>\u00a0is also impacted by substituents such as attached alkyl groups, whether the pi bond is interior or exterior to a ring (endocyclic \/ exocyclic) and attached heteroatoms.<\/p>\n<p>Back in the 1940s when UV-Vis was practically the only spectroscopic method available, Woodward and Fieser developed a set of empirical rules (the <a href=\"https:\/\/en.wikipedia.org\/wiki\/Woodward%27s_rules\">Woodward-Fieser rules<\/a>) that aim to predict the\u00a0\u03bb<sub>max\u00a0<\/sub>based on a number of structural factors. Variants of these rules for more complex conjugated systems also exist (<a href=\"http:\/\/pharmaxchange.info\/press\/2013\/05\/ultraviolet-visible-uv-vis-spectroscopy-\u2013-fieser-kuhn-rules-to-calculate-wavelength-of-maximum-absorption-lambda-max-of-polyenes-with-sample-problems\/\">Fieser-Kuhn rules<\/a>).<\/p>\n<p><strong><a id=\"notetwo\"><\/a>Note 2.<\/strong>\u00a0I would have liked to have used the UV-vis spectra of natural pigments like lycopene and chlorophyll as examples, but they contain more than one maximum. This isn&#8217;t easy to explain. Hence it isn&#8217;t as straightforward to translate into a color as Rhodamine B is. Here&#8217;s lycopene, for instance (source: wikipedia)<\/p>\n<p><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-15442\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-uv-vis-spectrum-of-lycopene-and-chlorophyll-have-multiple-absorption-maxima-not-as-easy-to-determine-color-wikipedia-image.png\" alt=\"uv vis spectrum of lycopene and chlorophyll have multiple absorption maxima not as easy to determine color wikipedia image\" width=\"450\" height=\"331\" srcset=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-uv-vis-spectrum-of-lycopene-and-chlorophyll-have-multiple-absorption-maxima-not-as-easy-to-determine-color-wikipedia-image.png 500w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-uv-vis-spectrum-of-lycopene-and-chlorophyll-have-multiple-absorption-maxima-not-as-easy-to-determine-color-wikipedia-image-300x221.png 300w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-uv-vis-spectrum-of-lycopene-and-chlorophyll-have-multiple-absorption-maxima-not-as-easy-to-determine-color-wikipedia-image-320x236.png 320w, https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/2019\/12\/F1-uv-vis-spectrum-of-lycopene-and-chlorophyll-have-multiple-absorption-maxima-not-as-easy-to-determine-color-wikipedia-image-360x265.png 360w\" sizes=\"(max-width: 450px) 100vw, 450px\" \/><\/p>\n<p><strong><a id=\"notethree\"><\/a>Note 3.<\/strong>\u00a0Also missing here is why UV-Vis spectra are broad and not straight lines. For instance, if, say, rhodamine has a delta E that corresponds to light of 560 nm, why does it also absorb light at 559 and 561 nm ? \u00a0Part of the answer is that the bonds are in constant vibration and this adjusts the value of delta E, so that a range of energies are absorbed.<\/p>\n<p><a id=\"notefour\"><\/a><strong>Note 4<\/strong>. [How far can we take this? At the far extreme, you have <a href=\"https:\/\/en.wikipedia.org\/wiki\/Graphene\">graphene<\/a>, which is just a big flat conjugated pi system with a near infinite number of conjugated\u00a0pi bonds. In this situation pretty much every wavelength of light corresponds to some kind of pi-pi* transition, and the result is a black color .]<\/p>\n<hr \/>\n<h2><a id=\"quizzes\"><\/a>Quiz Yourself!<\/h2>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3435-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3436-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3437-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/3438-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n\n<p class=\"p1\"><img loading=\"lazy\" decoding=\"async\" class=\"alignnone wp-image-26714\" src=\"https:\/\/www.masterorganicchemistry.com\/wp-content\/uploads\/quiz-previews\/2881-Front-Image-Only.png\" alt=\"\" width=\"640\" height=\"616\" \/><\/p>\n<p><a href=\"https:\/\/www.masterorganicchemistry.com\/moc-membership\/\"><strong>Become a\u00a0 MOC member<\/strong><\/a> to see the clickable quiz with answers on the back. <\/p>\n","protected":false},"excerpt":{"rendered":"<p>Understanding UV-Vis Spectroscopy Will Make You More Fun At Parties In today&#8217;s post we&#8217;ll discuss why most molecules are colourless, introduce the useful technique of <\/p>\n","protected":false},"author":1,"featured_media":15443,"comment_status":"open","ping_status":"open","sticky":false,"template":"","format":"standard","meta":{"_acf_changed":false,"footnotes":""},"categories":[386],"tags":[1122,1125,195,612,1124,1126,1123,1121,1120],"post_folder":[],"class_list":["post-10150","post","type-post","status-publish","format-standard","has-post-thumbnail","hentry","category-spectroscopy-2","tag-absorption-spectrum","tag-antibonding","tag-conjugation","tag-molecular-orbitals","tag-pi-orbitals","tag-pi-systems","tag-sigma-orbitals","tag-ultraviolet-spectroscopy","tag-uv-vis"],"acf":[],"yoast_head":"<!-- This site is optimized with the Yoast SEO plugin v27.7 - https:\/\/yoast.com\/product\/yoast-seo-wordpress\/ -->\n<title>What is UV-Vis Spectroscopy? 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