1. INTRODUCTION Nuclear chemistry deals with the structure of the nucleus and how this structure influences nuclear stability. It is also concerned with the ways the nucleus is changed, such as the processes of natural radioactivity and artificial nuclear transmutation. The energies involved in nuclear processes are several others greater than the energies released in ordinary chemical reactions because nuclear forces are correspondingly greater than chemical bonds.
Radiochemistry is the application of chemical methods to the study of radioactive substances
and the study of chemical effects of the radiation from radioactive materials. The difference between radiochemical and ordinary chemical procedures is the use of radioactive measurements. Information about the nature of the nucleus is derived from studying radioactivity.
Radioactivity is the spontaneous emission of radiation by radioactive elements.
The discovery of the phenomenon of radioactivity provided a means for investigating the internal structure of atoms, leading to the discovery of the atomic nucleus.
In 1896, while investigating the phosphorescence produced in various materials by lights, French physicist Henri Becquerel discovered radioactivity. Note that Phosphorescence is the emission of light of a certain wavelength by an object during and after excitation by light of another wavelength. The time lag distinguishes these effects from fluorescence.
Henri Becquerel used a uranium compound as one of his samples. Accidentally, he observed that this sample emitted rays without prior excitation by any kind of light. These highly energetic rays were capable of passing through several layers of materials which were opaque to ordinary light.
In 1898, Marie Curie, Becquerel’s student, found out that the radioactivity of a given uranium compound was independent of the specific compounds. The quantity of uranium present depends only on the quantity of Uranium present. Similarly, the thorium compound exhibits radioactivity, corresponding to the thorium content of the sample. She concluded that radioactivity is characteristic of setting elements rather than the compound of these elements. She and her husband, Piere Curie also noted that the level of radiation in naturally occurring uranium ore, called pitchblende, was much higher than could be explained by uranium content. Suspecting radioactivity in other elements, she discovered polonium and radium. 2.CHARACTERISTICS OF RADIATION FROM RADIOACTIVE MATERIALS ● A radioactive substance emits radiation continually and spontaneously. ● Temperature and pressure do not affect the rate at which radiation is emitted. ● The radiation, unlike light rays, can penetrate through opaque matter. ● It also ionises the gases through which it passes, causing fluorescence in certain materials like zinc sulphide leaving behind a track of cloud chamber. ● The energy of radioactivity is millions of times as great as that liberated during a chemical reaction. This energy is known as nuclear energy.
3. TYPES OF RADIATION The three main types of radiation are alpha, beta and gamma rays. When these radiations from a radioactive sample are passed through an electric field, the alpha rays are deflected towards the negative plate while the beta rays are deflected towards the positive plate. The alpha and beta rays are streams of charged particles with relatively large masses and momentum. The particles of the alpha are larger and hence are deflected to a smaller extent than the beta particles. The gamma rays are not affected by the electric field and are considered to have the highest penetrating power(energy) and are electromagnetic radiation similar to X-ray, UV-vis, infrared etc. Fig1
Table 1 Alpha Particle (α) The emission of an alpha particle (42He) from the nucleus of an atom results in the production of an atom of a new element, with an atomic and mass number less than 2 and 4 respectively. The emission of an alpha particle from a radium isotope is a good example: 88Ra ——→ 224 220 4 86Rn + 2He
Beta Particle (ꞵ)
● The emission of a negative beta particle, called negatron (0-1ꞵ) from a nucleus causes an increase of 1 in the atomic number, but no change in the mass number of the nucleus. 6C ——→ 7N + -1ꞵ 14 14 0
● The emission of a positively charged beta particle called a positron (0+1ꞵ) results in a decrease of 1 in atomic number and with no change in mass number. 11Na ——→ 10Ne + +1ꞵ 22 22 0
● Another radioactive process is the capture by the nucleus of an electron from the outside of the nucleus. This process is called electron capture (EC) or K capture because an electron in the 1s orbital (K-shell) of an atom is most likely to be captured. This process results in a decrease in atomic number but no change in mass number. It is similar to positron emission. Note that in K capture, the nucleus itself does not emit particles. There is radiation emitted from the atom because of an electron from the K shell. In the case of an X-ray of frequency corresponding to the energy difference between the two shells is emitted. The process is illustrated in Fig 2.
Most cases of alpha particle and beta particle emissions are accompanied by the emission of gamma rays.
Gamma-ray (γ) emission does not result in any change in the atomic number or mass number of the nucleus. Gamma rays are associated with a given nuclear transformation and have a definite energy, suggesting definite energy levels within the nucleus. In most nuclear transformations, the product nucleus is formed in an excited state and the process of transition from the excited state to the ground state. Gamma rays are emitted.
4. DETECTION OF RADIATION Different types of devices have been developed over the years for detecting radiation. The most commonly used are the ● Geiger-Müller Counter ● Scintillation counter ● Diffusion Cloud Chamber Exercise Explain the detection of radiation by Geiger-Muller Counter, Scintillation Counter and Diffusion Cloud Chamber. 5. NUCLEONS AND NUCLIDES A nuclide is any species of nucleus that has a specific atomic number and specific mass number. For instance, the 126C is an example of a nuclide.
14 6C is an isotope of carbon 126C both have the same atomic number, but they have different mass numbers. It is important to give the mass number and the atomic number because specific nuclides are always involved in nuclear phenomena.
The particles making up the nucleus, i.e., the protons and neutrons are called nucleons. The mass number is, therefore, the total number of nucleons (p and n) within the nucleus.
Nuclides have the same number of protons but different mass numbers, such as 126C and 146C, are called isotopes.
Nuclides having the same mass number but different such as 146C and 147N, are called isobars.
Nuclides, such as 146C and 147N however are not isotopic. 14 7N and 158O neither are isotopic nor isobaric, but their nuclei contain the same number of neutrons. Such species are called isotones of each other.
At present, there are about 1300 nuclei, which are distributed over 104 elements. There are 270 stable nuclides and the rest are radionuclides. Out of this number, 46 radionuclides occur in the decay series of uranium and thorium.
Radioactivity can be natural or artificial
6. NATURAL RADIOACTIVITY There are nuclides which have long half-lives comparable to the age of the earth and their decay products are found in nature.
Such radioactive elements emit alpha (42He) or beta (0-1e) particles giving rise to a new nucleus known as a daughter nucleus. The new daughter nucleus will have a mass of less than 4 and an atomic number of less than 2 and be found in two places to the left of the periodic table: 92U ——→ 90Th + 2He (α) 238 234 4
The emission of beta particles will give rise to a new daughter nucleus as the atomic number increases by 1. In the periodic table, it is placed one place to the right. 90Th ——→ 91Pa + -1e (ꞵ) 234 234 0
However, three of these series of such nuclides are as follows:
Uranium Series The nuclide 23892U half-life 4.5 x 10^9 years decays successively to another radionuclide until, after about 15 disintegrations through the same decay process thorium, a stable nuclide 20682Pb is formed. This is known as the 4n+2 series.
Thorium Series The nuclide, 23490Th with a half-life of 1.39 x 10^10 years decays successively to another radioactive nuclide (radionuclide) until after12 steps(disintegrations) through the emission of beta or alpha particle, a stable nuclide 20882Pb is formed. The mass number of each member of the series is exactly divisible by 4 and is sometimes designated as a 4n series.
Actinium Series This third series, known as the series, has 23592U as the parent nuclei. After about 13 disintegrations through the emission of beta or alpha particles, the terminal nuclei are 20782Pb. The series is also known as the 4n+ 3 series.
There is no evidence for a naturally occurring 4n+1 series of radioactive nuclides.
Other naturally occurring radioactive nuclides are summarised in the table below
Table 2
Nuclear Stability: The neutron-to-proton ratio determines the stability of nuclides. For stable atoms, it varies from 1 (unity) to about 1.5 for those heavier elements with atomic numbers from the 80s. Generally, atoms with proton-neutrons less than one or greater than 1.5 are considered to be unstable and radioactive. Although most naturally occurring light elements have stable nuclides. For example; 40K, 14C, etc. It is very common to observe radioactivity in the heavier elements from atomic number 82Pb to 92U.
7. HALF-LIFE AND RADIOACTIVITY DECAY.
The half-life of a radioactive element is the time taken for half of the total number of atoms in a given sample of the element to decay. That is, the time taken for half of the total number of samples to reduce to half. For 500 samples after some time (half-life) reduces to 250 and then another reduction same time to 125 and so on.
This number is continuously decreasing and so the process is referred to as radioactive decay. The equation for the decay process below
A ——→ B + X + ∆E The equation shows that a radioactive nuclide, A decays producing a nuclide B and particle X and some quantity of energy ∆E, which is given out.
The first law of radioactive decay is
Rate & N Rate = ᴧN -dN/dt = ᴧN ………………………………………………………………………. ……Eq(1) Where: N = number of atoms of the nuclide of atoms Rate = dN/dt is proportional to the number of atoms, N ᴧ = is the decay constant Hence: by rearrangement -dN/N = ᴧdt ……………………………………………………………………………. Eq(2)
By Integration N = No. e-ᴧt ………………………………………………………………………………Eq(3) Where No = Number of radioactive atoms at time t=0 N = number of remaining radioactive atoms after decay t= time taken ᴧ= decay constant
Therefore N = Nt Nt = No.e-ᴧt Which can be expressed as Nt = No (½)t/t½ ……………………………………………………….Eq(5) Where t½ = half-life.
If after one half-life t1/2, the fraction N/No becomes 0.5 or ½
Half-life and decay constant are related following first-order derivation:
2.3 x log 0.5 = -ᴧ t½
We have: ᴧ = 0.693/t1/2
Also t½ = 0.693/ᴧ …………………………………………………………………………….Eq(6)
8. ACTIVITY AND MASS
The radioactive nuclide depends on the activity of the substance and this is defined as the number of disintegration per unit time. The activity, A is merely the rate of decay and is proportional to the number of atoms present. A= dN/dt = ᴧN ……………………………………………………………………………Eq(7)
Similarly At = Ao.e-ᴧt ………………………………………………………………………………..Eq(8) Hence: At = Ao (½)t/t½ .....................................................................................................................Eq(9)
The Curie is the unit of radioactivity, defined as the quantity of any radioactive nuclide in which the number of disintegrations per second is 3.7x 1010. Therefore, 1 curie (1Ci) = 3.7 x 1010 dis/sec
1 millicurie (1mCi) = 3.7 x 107dis/sec
1microcurie (1uCi) = 3.7 x104dis/sec
1nanocurie (1nCi) = 37 dis/sec
The specific activity is defined as the number of disintegrations per unit time per gram of radioactive substance. Note: the unit of radioactivity is the Becquerel, which is defined as 1disintegration per second (1 dis/sec)
The equation A = -dN/dt = ᴧN
Hence N = A/ᴧ = A / (ln2 x t½) ………………………………………………………………….. Eq(10) Mass, m is given as m= N.M / NL ………………………………………………………………………………. Eq(11)
Substituting m = A. M / NL . ln2 . t½ …………………………………………………………………… Eq(12) Where M Molar mass and NL = Avogadro’s number.
9. NUCLEAR AND BINDING ENERGY
The nuclide mass M is the sum of the masses of proton mp and the neutron mN minus the quantity ∆m which corresponds to the binding energy of the nucleons in the nucleus as expressed mathematically: M = Zmp + NmN - ∆m ……………………………………………………………………….Eq(13) Where Z= number of protons N= number of neutrons
∆m is the mass defect which the binding energy can obtain using Einstein's equation E = ∆mc2…………………………………………………………………………………… Eq(14)
9.2. Nuclear Reactions
Artificial transmutation involves the bombardment of the nucleus by particles changing one element to another unlike natural radioactive. In 1909 Rutherford bombarded nitrogen gas with alpha particles and obtained hydrogen and Oxygen 7N + 2He ——→ 8O + 1H 14 4 17 1 9.3. Other Nuclear Transformation
(a) Nuclear Fission
In 1938, German scientists brought about nuclear fission by bombarding uranium-235 atoms with neutrons travelling at a moderate speed 92 + 0n ——→ 238 1 141 92 1 56Ba + 36Kr + 3 0n + Energy
The process in which the nucleus of heavy elements is split into two nuclei of nearly equal masses with the release of energy and radiation is called nuclear fission.
One of the applications of nuclear fission is used in atomic piles and atomic bombs. As the nuclear reaction continues, it leads to chain reactions. In order to sustain such a reaction, certain materials such as moderators are used to slow down the neutron so that at least one neutron from each 235U fission will bring about the fission process. Moderators such as Carbon graphite or heavy water are best used.
(b) Nuclear Fusion
When nuclei of light atoms combine to form heavy nuclei, we have new elements with the release of a large amount of energy. The amount of heat energy liberated by unit Mass in nuclear fusion is greater than that liberated by nuclear fission. The temperature for nuclear fusion is extremely high and can be described as a thermonuclear reaction.
Nuclear fusion is the process in which two or more light nuclei fuse to form a heavier nucleus with the release of energy and radiation. One of the applications is the production of hydrogen bomb 1H + 1H ——→ 2He + 0n + 17MeV (Energy) 2 3 4 1
2 1H + 21H ——→ 32He + 10n + 3.3MeV (Energy)
3 + 31H ——→ 4 2He + 2 10n + 11.3MeV (Energy) 1H Other applications of nuclear fusion are used to generate cheap sources of power and energy from the sun. Fig 3 10. APPLICATIONS OF RADIOACTIVITY 1. Radiochemical dating 2. Tracer studies 3. Medical uses 4. Industrial applications 5. Chemical analysis
Exercises Explain five applications of radioactivity with the following headings: i. Medical uses ii. Industrial uses iii. Agricultural uses iv. Tracers v. Chemical analysis
Further calculations 1. Starting with a 4.00mg sample, how much are 198Au remains after 7.0 days and 30 days? At what time does the amount of Au reach 0.40mg? [Given t½ of 198Au = 64.8hrs]
2. Calculate the binding energy of 42He [given the actual mass of He = 4.0026amu, mass of proton= 1.0078amu, neutron= 1.0087amu, c= 3.0x108m/s, 1amu= 1.6x10-27kg]
3. A bone of prehistory bison was found to have an activity of 3.8dis/min.g of Carbon. How long ago did the animal live? [Given t½ of 14C= 5668years, natural specific activity of 14C = 15.3dis/min.g]
References: C.L. Ndiokwere C.L. and M.E. Ukhun M.E. (2006), First-year university inorganic and physical chemistry. 3rd Edition, Mindex Publishing Company Limited, Benin City, Nigeria.
O. Y. Ababio (1998). New school chemistry for senior secondary school. 2nd Edition. Feb Africana Publishing Limited, Nigeria
