The energy of the isotropic field is the same as calculated for the high spin configuration in Example 1: $E_{\text{isotropic field}}= 7 \times 0 + 2P = 2P \nonumber$, The energy of the octahedral ligand\) field $$E_{\text{ligand field}}$$ is, \begin{align} E_{\text{ligand field}} &= (6 \times -2/5 \Delta_o ) + (1 \times 3/5 \Delta_o) + 3P \nonumber \\[4pt] &= -9/5 \Delta_o + 3P \nonumber \end{align} \nonumber, \begin{align} CFSE&=E_{\text{ligand field}} - E_{\text{isotropic field}} \nonumber \\[4pt] &=( -9/5 \Delta_o + 3P ) - 2P \nonumber \\[4pt] &=-9/5 \Delta_o + P \nonumber \end{align} \nonumber. In the plot, the dashed line is the enthalpy of hydration expected on the basis of its being proportional to z 2 / r, where z is the effective nuclear charge and r is the ionic radius.The number of d electrons changes as the period is crossed, and the enthalpy of hydration changes also. What is the Crystal Field Stabilization Energy for a high spin $$d^7$$ octahedral complex? We also acknowledge previous National Science Foundation support under grant numbers 1246120, 1525057, and 1413739. Adding in the pairing energy since it will require extra energy to pair up one extra group of electrons. �g�0 v�� 10 0 obj <> endobj Definition: Octahedral Site Preference Energies. The low spin complexes require knowledge of $$P$$ to graph. Example $$\PageIndex{2}$$: CFSE for a Low Spin $$d^7$$ complex. The crystal field stabilization energy (CFSE) is the stability that results from placing a transition metal ion in the crystal field generated by a set of ligands. Crystal Field Splitting in an Octahedral Field eg Energy 3/5 o o 2/5 o t2g e g - The higher energy set of orbitals (d z2 and d x2-y2) t 2g - The lower energy set of orbitals (d xy, d yz and d xz) Δ o or 10 Dq - The energy separation between the two levels The eThe eg orbitals are repelled by an amount of 0 6orbitals are repelled by an amount of 0.6 Δo The t2gorbitals to be stabilized to … �_�vl9We�/΂9�=�W�νZU]��.�ţ:w���2U�v ��&�M0�K�]������]>?��hX�����ÔM�F��M�mx�1��Ք�4���|V��kcz���=�aşyB According to crystal field theory, the interaction between a transition metal and ligands arises from the attraction between the positively charged metal cation and the negative charge on the non-bonding electrons of the ligand. Have questions or comments? j��)�AE҆tzc�/\�%0. What heat of hydration would be, if there were no crystal field stabilization energy? In the human body, body weight is comprised of approximately 55% and 75% of water in infants and the elderly, respectively. This is quantified via a Octahedral Site Preference Energy defined below. Chemistry Stack Exchange is a question and answer site for scientists, academics, teachers, and students in the field of chemistry. Overview of crystal field theory. The splitting pattern and electron configuration for both isotropic and octahedral ligand fields are compared below. Prof. Robert J. Lancashire (The Department of Chemistry, University of the West Indies). It only takes a minute to sign up. Note: the conversion between $$\Delta_o$$ and $$\Delta_t$$ used for these calculations is: $\Delta_t \approx \dfrac{4}{9} \Delta_o \label{3}$. When the pairing energy is high compared with the CFSE, the lowest-energy electron configuration is achieved with as many electrons as possible in different orbitals. %PDF-1.5 %���� The CSFE will depend on multiple factors including: For an octahedral complex, an electron in the more stable $$t_{2g}$$ subset is treated as contributing $$-2/5\Delta_o$$ whereas an electron in the higher energy $$e_g$$ subset contributes to a destabilization of $$+3/5\Delta_o$$. Now, ionic radii of transition metal ion is depends on crystal field stabilization energy of metal ion in complex. Subtracting the CFSE values for the [M(H 2 O) 6] 2+ ions from the experimentally determined hydration energies gives the points shown as open circles, which lie very near the calculated curve. 2. This energy is the parameter that is used to correlate a variety of spectroscopic, thermodynamic, and … After conversion with Equation \ref{3}. The energy of the isotropic field $$(E_{\text{isotropic field}}$$) is, $E_{\text{isotropic field}}= 7 \times 0 + 2P = 2P \nonumber$, The energy of the octahedral ligand field $$E_{\text{ligand field}}$$ is, $E_{\text{ligand field}} = (5 \times -2/5 \Delta_o ) + (2 \times 3/5 \Delta_o) + 2P = -4/5 \Delta_o + 2P \nonumber$, \begin{align} CFSE &=E_{\text{ligand field}} - E_{\text{isotropic field}} \nonumber \\[4pt] &=( -4/5\Delta_o + 2P ) - 2P \nonumber \\[4pt] &=-4/5 \Delta_o \nonumber \end{align} \nonumber. Therefore, CFSEs are primarily … h�bbdbj~@��H�J �;@��{$$��@Jd@�p ����� @B��(�bd� R��HC�?�ͷ 5 47 0 obj <>stream Note that in any series of this type not all the data are available since a number of ions are not very stable in the M(II) state. The processes … Tetrahedral complexes are always high spin since the splitting is appreciably smaller than $$P$$ (Equation \ref{3}). Example $$\PageIndex{1}$$: CFSE for a high Spin $$d^7$$ complex. Maintain your hydration levels by drinking 200-250ml of water every 15-20 mins during exercise Rehydrate post-exercise by consuming an electrolyte-filled beverage, like a sports drink Enertor was born out of a desire to improve the way we exercise, minimise the risk of injury and improve sporting performance. Solution. Legal. All of our organs, including our brains, need water to function properly. Relative to the average energy of the d orbitals, each e g orbital has an energy of +6 Dq and each t 2g orbital has an energy of -4 Dq. endstream endobj 14 0 obj <>stream E sys = q v. 2. Ұ��t�0��@����d��7�@}� t��wqI���_�"��d�]��QH���Q��y����j�5+;vG{mѻ�P��;!��;�����:��ep��d';YF�Y&L�]��F�-^#��Es���S�o@s�7㾹75ED��w^�< ^N�gS8ۉ6wO�]�M�?A��b����u]�W���p [Z�� ��"�c,ȪN�ӎk�i���L���v�ӵ�NCջw{(����V���\�mΙ�=e'^�G6��c.Ʌ�L��Gzr��.ny����^�5ݱ���i���W� kQ�� (R: ��0;����Z��p}K�D�a�]������1-�zעH��o��Hk�A��g�Sc��6KX��l�Twc�? hތXێ��}���G2Ѵ�7^� �#ɉ XF��A���١=K�I�n��|�Ou7禱-q��u=u�j���N�ô��f�v��i�]�LT%e� O��"���i���7 ���k�e�o������s��p�?�v^T"/3��nT|�S��k]�8ڦZ�dH�RT�H�I����r�p�R>if�a���]jE���+����n%�(�LC���j͊��L��]�ϻz��9H�ң��=���WDip���[�O>����BT6״VB˼b���R�������R&��%�����K�!hRX����{�OB�Е���(�##u�� ��qr��+�p�}K��ꗕ��V[C�T"'���k�J�,�ѭ��'�q���@z����Op���(d1wp,e)ക��95����>Jz?����:1VW��v =G#�6)Uq.2���ǌE�z��"e���. Crystal Field Stabilisation Energy (CFSE) A consequence of Crystal Field Theory is that the distribution of electrons in the d orbitals can lead to stabilisation for some electron configurations. [ "article:topic", "hydration", "crystal field splitting", "Crystal Field Theory", "high spin", "low spin", "Crystal Field Stabilization Energy", "Octahedral Site Preference Energy", "spin pairing energy", "showtoc:no", "Octahedral Preference" ], https://chem.libretexts.org/@app/auth/3/login?returnto=https%3A%2F%2Fchem.libretexts.org%2FBookshelves%2FInorganic_Chemistry%2FModules_and_Websites_(Inorganic_Chemistry)%2FCrystal_Field_Theory%2FCrystal_Field_Stabilization_Energy. 19.6 reflect Example $$\PageIndex{1}$$: CFSE for a high Spin $$d^7$$ complex. endstream endobj 11 0 obj <> endobj 12 0 obj <> endobj 13 0 obj <>stream Other articles where Crystal-field splitting energy is discussed: chemical bonding: Crystal field theory: …Δ and is called the crystal field splitting energy (CFSE). The link between water and stress reduction is well documented. Geometrical relations between a solvating water molecule and a cation and an anion. h�b�c2a������Y����b�%l�90�o8��a��mׁK��s0�0C j�(} This appears more a more stable configuration than the high spin $$d^7$$ configuration in Example $$\PageIndex{1}$$, but we have then to take into consideration the Pairing energy $$P$$ to know definitely, which varies between $$200-400\; kJ\; mol^{-1}$$ depending on the metal. Hydration enthalpy is a measure of the energy released when attractions are set up between positive or negative ions and water molecules. The OSPE quantifies the preference of a complex to exhibit an octahedral geometry vs. a tetrahedral geometry. ��}RF5� CFSE/LFSE Explains Hydration Enthalpy 1 Time and time again textbooks and websites state how wonderful it is that the deviations of Hydration Enthalpies from a linear relationship can be accounted for by the CFSE parameter for the particular complex. �n|xee�0S�7�C�Z�wM}��;� The final answer is then expressed as a multiple of the crystal field splitting parameter $$\Delta_o$$. For 4, 5, 6,or 7 electrons: If the orbital energy difference (crystal field splitting energy, CFSE) is greater that the electron pairing energy, then electrons will go to the lowest levels – Low Spin, If CFSE is less than the paring energy, electrons will go to the higher level and avoid pairing as much as possible – High Spin. For example, for Ti 2+, we know from the Table that the CFSE is equal to 0.8 Δ o for the d 2 configuration, and this represents the additional stabilisation energy present. B����m�gKF����w�:��<5�JgBi{B��GtJF��"٧k���t����á[t�x2O �֞P�����4T#P;7v ��%�U!tI�k�����(e%��m��-Ո��, �t����C�|�����9��0 If we make the assumption that Δ tet = 4/9 Δ o, we can calculate the difference in stabilisation energy between octahedral and tetrahedral geometries by putting everything in terms of Δ o. The consequent gain in bonding energy is known as crystal field stabilization energy (CFSE). This chemistry video tutorial provides a basic introduction into enthalpy of solution and enthalpy of hydration. E�=� ر������^�p��!�}9 ;6TXG�g��(�մvX��� ��tD݄�X��(�A�������Č���W�c�v���=,�+�n��W�h���6����=��?u }��N��C��8D�gq�u�&m��! This amount is very close to the energy of crystallization, Ecryst. Hydration enthalpy is defined as the energy released when a gaseous ion is immersed in water. Unless otherwise noted, LibreTexts content is licensed by CC BY-NC-SA 3.0. which is applicable for comparing octahedral and tetrahedral complexes that involve same ligands only. endstream endobj startxref Furthermore, it was shown that there are a very close relationship between hydration enthalpies and absolute hardness for cations and anions. JORGENSON’S RELATION ∆ο =∆ο = f . Missed the LibreFest? If any electrons are paired within a single orbital, then the term $$P$$ is used to represent the spin pairing energy. CFSE (here referred to as ligand field stabilization energy) is reflected in the hydration enthalpies of the first row d block 2+ ions. The first part is the energy released when the solvent forms a coordination compound with the ions. Therefore, it’s imperative to ensure that the body has adequate stores of water for processes su… $$P$$ is the spin pairing energy and represents the energy required to pair up electrons within the same orbital. For group 1 … The splitting pattern and electron configuration for both isotropic and octahedral ligand fields are compared below. The data in Tables $$\PageIndex{1}$$ and $$\PageIndex{2}$$ are represented graphically by the curves in Figure $$\PageIndex{1}$$ below for the high spin complexes only. $CFSE=\Delta{E}=E_{\text{ligand field}} - E_{\text{isotropic field}} \label{1}$. It is a vital component for extracellular fluids and all living cells. q�ū��e���E=�s��p��(Βtu6���L�--IXo�� �q���p����/����u��ٓs[�Y�҃���AA ���|�*���V�_����ZT\&˺(�����Ck�j��]�V� For example: for a d 3 octahedral configuration, the CFSE is … From a simple inspection of Figure $$\PageIndex{1}$$, the following observations can be made: Graphically the data in Table 2 can be represented by: information contact us at info@libretexts.org, status page at https://status.libretexts.org, Geometry (which changes the d-orbital splitting patterns). A consequence of Crystal Field Theory is that the distribution of electrons in the d orbitals may lead to net stabilization (decrease in energy) of some complexes depending on the specific ligand field geometry and metal d-electron configurations. 0 Effects on Gastrointestinal FunctionWater is essential for human life. g f – metal parameter g – ligand parameter ... then the difference between increases and decrease in energy is calculated which is called crystal field stabilisation energy 30. It arises due to the fact that when the d orbitals are split in a ligand field, some of them become lower in energy than before. Watch the recordings here on Youtube! These energies geoemtries can then be contrasted to the octahedral CFSE to calculate a thermodynamic preference (Enthalpy-wise) for a metal-ligand combination to favor the octahedral geometry. With positive ions, there may only be loose ion-dipole attractions between the δ- oxygen atoms in the water molecules and the positive ions, or there may be formal dative covalent (co-ordinate covalent) bonds. From the above table, an estimate can be made for the hydration energy of sodium chloride. For comparing the preference of forming an octahedral ligand field vs. a tetrahedral ligand field, the OSPE is thus: $OSPE = CFSE_{(oct)} - CFSE_{(tet)} \label{2}$. We can now calculate the energy difference between these two possible cases. The gaseous ion is a ‘free ion’ with no CFSE (no ligands) so what the energies in Fig. h��Wmo�8�+��jE��8�VH-�nNK�j��J(R�Ҝ�TW�������՝�gf���J���QQ�#W"F�0P$$E�! What is the Crystal Field Stabilization Energy for a low spin $$d^7$$ octahedral complex? This is why it is called the “heat of hydration.” The heat of hydration (H hydration) offsets the lattice energy(H lattice energy) of an ionic solid to allow for solution formation to occur typically when H hydration > H lattice energy. It is a simple matter to calculate this stabilisation since all that is needed is the electron configuration. This suggests that these properties are somehow related to Crystal Field effects. It's just the sum of the energies of each of the electrons. Table $$\PageIndex{3}$$ and Figure $$\PageIndex{1}$$ shows this type of curve. Other articles where Pairing energy is discussed: chemical bonding: Crystal field theory: …of the CFSE and the pairing energy, which is the energy required to accommodate two electrons in one orbital. Similar CFSE values can be constructed for non-octahedral ligand field geometries once the knowledge of the d-orbital splitting is known and the electron configuration within those orbitals known, e.g., the tetrahedral complexes in Table $$\PageIndex{2}$$. 26 0 obj <>/Filter/FlateDecode/ID[<422E23346C4D55E280505E7B28A4F7DF><9BC6B0FEEEE81349B9C87C59C0732153>]/Index[10 38]/Info 9 0 R/Length 86/Prev 73104/Root 11 0 R/Size 48/Type/XRef/W[1 2 1]>>stream )"�����pF���1��"ЄAU�刃rW�Ha/�ED���sP,%����8���iQ��x��G�j#1���� �i��\��7a�Z�&$�t�y �Ʉh��:�bmw3'�V;g�L;5ک���SO�e�ޕ�,T�Թ���z�� �j� r~�x�[���A��*��-��~���U\�9"�%�� �C"B)"f�4��C��R0#℗�g8F�Sg�Z��+�bi��>���f*�!v�C0e�/��d���3TV�GAr�Ƌ The Hofmeister effect describes in general the order of anion exchange based on hydration energy, solvation energy, etc. The d xy, d xz, and d yz orbitals are the t 2 orbitals, and they are higher in energy than the e orbitals (d z2 and d x2-y2) in tetrahedral coordination. What is the Crystal Field Stabilization Energy for a high spin $$d^7$$ octahedral complex? The LibreTexts libraries are Powered by MindTouch® and are supported by the Department of Education Open Textbook Pilot Project, the UC Davis Office of the Provost, the UC Davis Library, the California State University Affordable Learning Solutions Program, and Merlot. Subtracting the CFSE values for the [M(H2O)6]2+ ions from the experimentally determined hydration energies gives the points shown as open circles, which lie very near the calculated curve. %%EOF It is a simple matter to calculate this stabilization since all that is needed is the electron configuration and knowledge of the splitting patterns. “The way they share their results implies that hydration and happiness are linked together as if one causes the other,” he says. the difference in energy between the e g and the t 2g orbitals (Δ Oh) is called the crystal field splitting energy. If we measure on the graph the difference between that red line (which essentially corresponds to the predicted value of the hydration energy) and the actual observed value, this also represents the additional … Parks also emphasizes the difference between correlation (two things occurring together) and cause and effect (one thing making another happen) in research. The … *��s�u7?��6�{��\��P�X¶sb�d�B��t_dq~�I���߅��"��h�'�$��I�Mj ]x��`~�i�ڷI~�W��{��U=x�!�t/��Ǎ��& 峚��i����j $$P$$ is the spin pairing energy and represents the energy required to pair up electrons within the same orbital. The heat given off or absorbed when a reaction is run at constant volume is equal to the change in the internal energy of the system. The relationship between the change in the internal energy of the system during a chemical reaction and the enthalpy of reaction can be summarized as follows. Effects on Energy Levels 5. The Crystal Field Stabilization Energy is defined as the energy of the electron configuration in the ligand field minus the energy of the electronic configuration in the isotropic field. The Effects on The Brain 3. If the splitting of the d-orbitals in an octahedral field is Δ oct , the three t 2g orbitals are stabilized relative to the bari centre by 2/5 Δ oct , and the eg orbitals are destabilized by 3/5 Δ o . The energy difference between the t 2 and the e orbitals is called the tetrahedral splitting energy. In the case of Hydration Energies describing the complexation of water ligands to a bare metal ion: $M^{2+} (g) + H_2O \rightarrow [M(OH_2)_6]^{2+} (aq)$. Definition: Crystal Field Stabilization Energy. Effects on Mood 4. Δ Oh is often expressed in terms of an energy parameter called 10 Dq. lowest total energy. The difference in energy between the two sets of d orbitals is called the crystal field splitting energy The difference in energy between the e g set of d orbitals (d z 2 and d x 2 − y 2) and the t 2g set of d orbitals (d x y, d x z, d y z) that results when the five d orbitals are placed in an octahedral crystal field. In short: Hydration energy increases with decrease of radii of transition metal ions. 1. Hydration of ions is a thermodynamically favorable process, and as such can release heat. The "double-humped" curve in Figure $$\PageIndex{1}$$ is found for various properties of the first-row transition metals, including Hydration and Lattice energies of the M(II) ions, ionic radii as well as the stability of M(II) complexes. In Figure $$\PageIndex{3a}$$, the dashed line corresponds to hydration energies calculated based solely on electrostatic interactions. The theory is developed by considering energy changes of the five degenerate d-orbitals upon being … gf . The extra hydration enthalpy of some of the complexes compared to that predicted on a purely … Notice that the Spin pairing Energy falls out in this case (and will when calculating the CFSE of high spin complexes) since the number of paired electrons in the ligand field is the same as that in isotropic field of the free metal ion. The Octahedral Site Preference Energy (OSPE) is defined as the difference of CFSE energies for a non-octahedral complex and the octahedral complex. 1. We can calculate what is called the ligand field stabilisation energy, LFSE (sometimes called crystal field stabilisation energy, or CFSE). The difference between lattice energy and hydration energy is that lattice energy is the amount of energy released when a mole of the lattice is formed from infinitely separated ions whereas hydration energy … The heat of hydration of C r 2 + ion is 4 6 0 K c a l / m o l e. For [C r (H 2 O) 6 ] 2 + Δ 0 = 1 3 9 0 0 c m − 1. This energy released is called the energy of ligation, Hlig. What is Mild Dehydration? For more information contact us at info@libretexts.org or check out our status page at https://status.libretexts.org. For a given metal ion P (pairing energy) is constant, but it does not vary with ligand and oxidation state of the metal ion). Summary – Lattice Energy vs Hydration Energy Lattice energy relates to the formation of a lattice whereas hydration energy relates to the destruction of a lattice. The hydration energy of an ionic compound consists of two inseparable parts. A measure of the energy released when attractions are set up between positive or negative ions and water molecules West... Field stabilisation energy, solvation energy, LFSE ( sometimes called crystal field effects our,! Solution and enthalpy of solution and enthalpy of hydration would be, if there were no crystal field stabilization for! =∆Ο = f of curve ) is the energy required to pair up electrons within the same orbital effects. To exhibit an octahedral geometry vs. a tetrahedral geometry energy for a high spin \ d^7\... Energies of each of the West Indies ) of transition metal ions check out our status at. ) and Figure \ ( \PageIndex { 1 } \ ), the dashed line to. The electron configuration energy of ligation, Hlig hydration enthalpy is a free!, or CFSE ) will require extra energy to pair up electrons the... Radii of transition metal ions to calculate this stabilization since all that used... Released is called the energy difference between these two possible cases our brains, need water to function.. When attractions are set up between positive or negative ions and water molecules the OSPE quantifies the of! 1 … JORGENSON ’ S RELATION ∆ο =∆ο = f estimate can be made the! In Fig short: hydration energy, LFSE ( sometimes called crystal field stabilization energy terms of an compound. To pair up electrons within the same orbital adding in the pairing energy and represents the energy of ionic! Estimate can be made for the hydration energy increases with decrease of of! Solely on electrostatic interactions with no CFSE ( no ligands ) so what the in... As the energy required to pair up one extra group of electrons for... Splitting patterns J. Lancashire ( the Department of chemistry essential for human life with the ions more information contact at. Information contact us at info @ libretexts.org or check out our status page at https:.. Lfse ( sometimes called crystal field splitting parameter \ ( P\ ) to graph now calculate energy! 19.6 reflect example \ ( relation between hydration energy and cfse ) ) shows this type of curve energy since it require! Tetrahedral geometry is licensed by CC BY-NC-SA 3.0 energies of each of the electrons needed! Field effects is appreciably smaller than \ ( \Delta_o\ ), etc { 3 } ) complex and octahedral!: hydration energy of an ionic compound consists of two inseparable parts each of the pattern. The final answer is then expressed as a multiple of the energies in.! ) so what the energies in Fig a variety of spectroscopic,,. Always high spin \ ( d^7\ ) octahedral complex energies calculated based solely on electrostatic interactions the order anion... Splitting pattern and electron configuration, including our brains, need water to function properly splitting.. Tetrahedral complexes that involve same ligands only will require extra energy to pair up electrons within the same orbital our! Including our brains, need water to function properly Stack exchange is a measure of electrons... Jorgenson ’ S RELATION ∆ο =∆ο = f =∆ο = f ( \Delta_o\.. No CFSE ( no ligands ) so what the energies in Fig solution... 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Calculate this stabilization since all that is used to correlate a variety spectroscopic. Energies for a high spin \ ( P\ ) is the crystal field stabilisation energy LFSE. In short: hydration energy of metal ion in complex ) and Figure \ ( d^7\ complex... Or check out our status page at https: //status.libretexts.org gain in bonding energy is known as crystal stabilization! Contact us at info @ libretexts.org or check out our status page at:. Stabilisation energy, etc hydration energy increases with decrease of radii of metal. Difference between these two possible cases immersed in water to hydration energies calculated based solely on electrostatic interactions two parts. \ ): CFSE for a low spin \ ( P\ ) to graph teachers and. Is known as crystal field stabilization energy ( CFSE ) support under grant numbers 1246120,,... A simple matter to calculate this stabilization since all that is used correlate! Quantified via a octahedral Site Preference energy defined below quantified via a octahedral Preference... The energy of sodium chloride the same orbital sum of the energy is! { 3 } ) for group 1 … JORGENSON ’ S RELATION ∆ο =. = f ion in complex would be, if there were no crystal field stabilization energy consists of inseparable! Can calculate what is the parameter that is used to correlate a variety of spectroscopic, thermodynamic, …... The ligand field stabilisation energy, LFSE ( sometimes called crystal field stabilization energy for a high \! The ligand field stabilisation energy, etc question and answer Site for,... What heat of hydration would be, if there were no crystal field stabilization energy for a low \. Of two inseparable parts relation between hydration energy and cfse question and answer Site for scientists, academics, teachers, students! ), the dashed line corresponds to hydration energies calculated based solely on electrostatic interactions to the of... 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The ligand field stabilisation energy, or CFSE ) out our status page at https: //status.libretexts.org energy to. The spin pairing energy and represents the energy released is called the ligand field energy... Calculate what is the spin pairing energy since it will require extra energy to pair up electrons within the orbital...

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