beer lambert law

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beer lambert law

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relates the absorption of light to the properties of the material through which the light is traveling.

Equations

The law states that there is a logarithmic dependence between the transmission (or transmissivity), T, of light through a substance and the product of the absorption coefficient of the substance, , and the distance the light travels through the material (i.e. the path length), . Theabsorption coefficient can, in turn, be written as a product of either a molar absorptivity (extinction coefficient) of the absorber, , and theconcentration c of absorbing species in the material, or an absorption cross section, , and the (number) density N' of absorbers. For liquids, these relations are usually written as:

whereas for gases, and in particular among physicists and for spectroscopy and spectrophotometry, they are normally written

where I0 and I are the intensity (or power) of the incident light and the transmitted light, respectively; is cross section of light absorption by a single particle and N is the density (number per unit volume) of absorbing particles. The base 10 and base e conventions must not be confused because they give different values for the absorption coefficient: using . However, it is easy to convert one to the other, .

The transmission (or transmissivity) is expressed in terms of an absorbance which, for liquids, is defined as

This implies that the absorbance becomes linear with the concentration (or number density of absorbers) according to

and

for the two cases, respectively. Thus, if the path length and the molar absorptivity (or the absorption cross section) are known and the absorbance is measured, the concentration of the substance (or the number density of absorbers) can be deduced. Although several of the expressions above often are used as BeerLambert law, the name should strictly speaking only be associated with the latter two. The reason is that historically, the Lambert law states that absorption is proportional to the light path length, whereas the Beer law states that absorption is proportional to the concentration of absorbing species in the material.[1] If the concentration is expressed as a mole fraction i.e. a dimensionless fraction, the molar absorptivity () takes the same dimension as the absorption coefficient, i.e. reciprocal length (e.g. m1). However, if the concentration is expressed in moles per unit volume, the molar absorptivity () is used in Lmol1cm1, or sometimes in converted SI units of m2mol1. The absorption coefficient ' is one of many ways to describe the absorption of electromagnetic waves. For the others, and their interrelationships, see the article: Mathematical descriptions of opacity. For example, ' can be expressed in terms of the imaginary part of the refractive index, , and the wavelength of the light (in free space), 0, according to

In molecular absorption spectrometry, the absorption cross section is expressed in terms of a linestrength, S, and an (area-normalized) lineshape function, . The frequency scale in molecular spectroscopy is often in cm1, wherefore the lineshape function is expressed in units of 1/cm1, which can look funny but is strictly correct. Since N is given as a number density in units of 1/cm3, the linestrength is often given in units of cm2cm1/molecule. A typical linestrength in one of the vibrational overtone bands of smaller molecules, e.g. around 1.5 m in CO or CO2, is around 1023 cm2cm1, although it can be larger for species with strong transitions, e.g. C2H2. The linestrengths of various transitions can be found in large databases, e.g. HITRAN. The lineshape function often takes a value around a few 1/cm1, up to around 10/cm1 under low pressure conditions, when the transition is Doppler broadened, and below this under atmospheric pressure conditions, when the transition is collision broadened. It has also become commonplace to express the linestrength in units of cm2/atm since then the concentration is given in terms of a pressure in units of atm. A typical linestrength is then often in the order of 103 cm2/atm. Under these conditions, the detectability of a given technique is often quoted in terms of ppmm. The fact that there are two commensurate definitions of absorbance (in base 10 or e) implies that the absorbance and the absorption coefficient for the cases with gases, A' and ', are ln 10 (approximately 2.3) times as large as the corresponding values for liquids, i.e. A and , respectively. Therefore, care must be taken when interpreting data that the correct form of the law is used.

The law tends to break down at very high concentrations, especially if the material is highly scattering. If the light is especially intense, nonlinear optical processes can also cause variances.

Attenuation coefficient

The attenuation coefficient is a quantity that characterizes how easily a material or medium can be penetrated by a beam of light, sound, particles, or other energy or matter. A large attenuation coefficient means that the beam is quickly "attenuated" (weakened) as it passes through the medium, and a small attenuation coefficient means that the medium is relatively transparent to the beam. Attenuation coefficient is measured using units of reciprocal length. The attenuation coefficient is also called linear attenuation coefficient, narrow beam attenuation coefficient, or absorption coefficient. Although all four terms are often used interchangeably, they can occasionally have a subtle distinction, as explained below. The attenuation coefficient describes the extent to which the intensity of an energy beam is reduced as it passes through a specific material. This might be a beam of electromagnetic radiation orsound. It is used in the context of X-rays or Gamma rays, where it is represented using the symbol , and measured in cm . It is also used for modeling solar and infrared radiative transfer in the atmosphere, albeit usually denoted with another symbol (given the standard use of = cos() for slant paths). In the case of ultrasound attenuation it is usually denoted as and measured in dB/cm/MHz. The attenuation coefficient is widely used in acoustics for characterizing particle size distribution.

[1][3] [1][2] 1

A common unit in this contexts is inverse metres, and the most common symbol is

the Greek letter . It is also used in acoustics for quantifying how well a wall in a building absorbs sound. Wallace Sabine was a pioneer of this concept. A unit named in his honor is the sabin: the absorption by a 1-square-metre (11 sq ft) slab of perfectly-absorptive material (the same amount of sound loss as if there were a 1-square-metre window).

[4]

coefficient; rather, it is the unit of a related quantity. A small linear attenuation coefficient indicates that the material in question is relatively transparent, while a larger values indicate greater degrees of opacity. The linear attenuation coefficient is dependent upon the type of material and the energy of the radiation. Generally, for electromagnetic radiation, the higher the energy of the incident photons and the less dense the material in question, the lower the corresponding linear attenuation coefficient will be

The measured intensity I of transmitted through a layer of material with thickness x is related to the incident intensity I0 according to the inverse exponential power law that is usually referred to asBeer Lambert law:

where x denotes the path length. The attenuation coefficient (or linear attenuation coefficient) is . The Half Value Layer (HVL) signifies the thickness of a material required to reduce the intensity of the emergent radiation to half its incident magnitude. It is from these equations that engineers decide how much protection is needed for "safety" from potentially harmful radiation. The attenuation factor of a material is obtained by the ratio of the emergent and incident radiation intensities I / I0. The linear attenuation coefficient and mass attenuation coefficient are related such that the mass attenuation coefficient is simply / , where is the density in g/cm . When this

3

coefficient is used in the Beer-Lambert law, then "mass thickness" (defined as the mass per unit area) replaces the product of length times density. The linear attenuation coefficient is also inversely related to mean free path. Moreover, it is very closely related to the absorption cross section.

The terms "attenuation coefficient" and "absorption coefficient" are generally used interchangeably. However, in certain situations they are distinguished, as follows.

[5]

When a narrow (collimated) beam of light passes through a substance, the beam will lose intensity due to two processes: The light can be absorbed by the substance, or the light can be scattered(i.e., the photons can change direction) by the substance. Just looking at the narrow beam itself, the two processes cannot be distinguished. However, if a detector is set up to measure light leaving in different directions, or conversely using a non-narrow beam, one can measure how much of the lost intensity was scattered, and how much was absorbed. In this context, the "absorption coefficient" measures how quickly the beam would lose intensity due to the absorption alone, while "attenuation coefficient" measures the total loss of narrow-beam intensity, including scattering as well. "Narrow-beam attenuation coefficient" always unambiguously refers to the latter. The attenuation coefficient is always larger than the absorption coefficient, although they are equal in the idealized case of no scattering

Question : What is the significance of the molar absorbtivity, ? Answer : To begin we will rearrange the equation A = bc :

= A / bc In words, this relationship can be stated as " is a measure of the amount of light absorbed per unit concentration". Molar absorbtivity is a constant for a particular substance, so if the concentration of the solution is halved so is the absorbance, which is exactly what you would expect. Let us take a compound with a very high value of molar absorbtivity, say 100,000 L mol-1 cm-1, which is in a solution in a 1 cm pathlength cuvette and gives an absorbance of 1. = 1 / 1 c Therefore, c = 1 / 100,000 = 1 -5 mol L-1 Now let us take a compound with a very low value of , say 20 L mol-1 cm-1 which is in solution in a 1 cm pathlength cuvette and gives an absorbance of 1. = 1 / 1 c Therefore, c = 1 / 20 = 0.05 mol L-1 The answer is now obvious - a compound with a high molar absorbtivity is very effective at absorbing light (of the appropriate wavelength), and hence low concentrations of a compound with a high molar absorbtivity can be easily detected.

In spectroscopy, the absorbance A (also called optical density)[2][3] is defined as:[4] , where I is the intensity of light at a specified wavelength that has passed through a sample (transmitted light intensity) and I0 is the intensity of the light before it enters the sample or incident lightintensity (or power). Absorbance measurements are often carried out in analytical chemistry, since the absorbance of a sample is proportional to the thickness of the sample and the concentration of the absorbing species in the sample, in contrast to the transmittance I / I0 of a sample, which varies exponentially with thickness and concentration

optical density (OD): For a given wavelength, an expression of the transmittance of an optical element. Note 1: Optical density is expressed by log 10(1/T) where T is transmittance. Note 2: The higher the optical density, the lower the transmittance. Note 3: Optical density times 10 is equal to transmission loss expressed in decibels, e.g., an optical density of 0.3 corresponds to a transmission loss of 3 dB

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