冠醚配合物的热力学性质的研究 III. 碱金属离子与18C6甲基衍生物配位反应的电导研究

The coordination reaction of Na+, K+, Rb+ and Cs+ with benzo- 15-crown-5, 18-crown-6 and the newly synthesized cyclic polyethers 2, 3-benzo-8, 15-dimethyl-18-crown-6, 2, 3-benzo-8, 11, 15-trimethyl-18-crown-6 in methanol at 25`C has been studied by conductometric titration. The stability constants for the 1:1 coordination compounds were calculated. The marked selectivity of 18-crown-6 toward alkali metal ions was not found in its methyl derivatives. The induction effect of the benzene ring and methyl group on polyether ring reduced the stability of the coordination compounds. In methanol, the stability sequence of te compounds of alkali metal ions with 18-crown-6 was K+>Rb+>Cs+>Na+, that of its dimethyl derivative was K+>Rb+>Na+>Cs+ and that of its trimethyl derivative was K+>Na+>Rb+>Cs+, that is, the methyl substituent had a weaker influence on the stability of Na+ compound than on that of Rb+ or Cs+ compound. In the range of concentration studied, decrease in equivalent conductance is in agreement with the prediction on the basis of the structure of the complexes. The above results may give a clue for modifying the structure of a crown ether for specified selectivity.     

Bifunctional potentiometric sensor based on MoO3 nanorods

A solid-phase film electrode with an ion-sensitive membrane based on MoO₃ nanorods was developed. Depending on the pH of test solution, the proposed electrode can be used as a sensor for measuring the concentration of hydrogen or alkali metal ions. In the range of 1 ≤ pH ≤ 5, the electrode reacts to changes in the concentration of hydrogen ions with an electrode response slope of 54 ± 2 mV/pH. The electrode is selec- tive to alkali metal cations in the concentration ranges of $0 \leqslant pc_{M^ + } \leqslant 4$ for M = Na, K, and Li and $1 \leqslant pc_{M^ + } \leqslant 5$ for M = Rb and Cs and the solution acidity 5 ≤ pH ≤ 13.5 with a nearly theoretical slope. The selectivity coefficients of the electrode to the ions of Na(I), Rb(I), Cs(I), Mg(II), Ca(II), Sr(II), and Ba(II) were determined.     

Gibbs energies of transfer of alkali metal cations between mutually saturated water-solvent systems determined from extraction experiments with radiotracer 137Cs

Thermodynamic standard Gibbs energies of transfer of alkali metal cations related to Cs+ cation [DeltatG degrees*,(Cs+)-[DeltatG degrees*,(M+)] between several mutually saturated solvents of the type water-solvent were calculated from determined extraction exchange constants Kexch degrees,*(Cs+/M+). The used liquid-liquid extraction method with radioactive tracing by 137Cs permits attaining higher precision of the values as compared to the methods used up to now. The data for o-nitrophenyloctyl ether, 1,2-dichloroethane, and 1-octanol were compared with literature sources and recommended absolute values of DeltatG degrees,*M+) are reported. For dissociating solvents, the dependences of [DeltatG degrees,*(Cs+) - [DeltatG degrees,*(M+)] on Gibbs energy of hydration of an ion, DeltaGhydr degrees are straight lines either for four cations Cs+, Rb+, K+, and Na+ (nitrosolvents) or for three cations Cs+, Rb+, and K+ (1,2-dichloroethane and 1-octanol). The hydration of Na+ and still more of Li+ in the water-saturated organic phase is apparent from the results. This manifests for high-water-content equilibrium 1-octanol even in a reversal of the values [i.e., DeltatG degrees*,(Li+) being more negative than DeltatG degrees,*(Na+)], although for Cs+, Rb+, and K+, the general trend is conserved. Water-saturated 1-octanol is thus slightly less basic than water, but the overall selectivity is very low. For one studied nondissociating solvent, dioctyl sebacate, the trend of the dependences of log Kexch degrees,*(CsB/M+) on DeltaGhydr degrees is similar to that of Kexch degrees,*(Cs+/M+) for polar solvents, but different for different anions B, thus reflecting ion association in the organic phase.     

Artificial ion channel formed by cucurbit[n]uril derivatives with a carbonyl group fringed portal reminiscent of the selectivity filter of K+ channels

Novel artificial ion channels (1 and 2) based on CB[n] (n = 6 and 5, respectively) synthetic receptors with carbonyl-fringed portals (diameter 3.9 and 2.4 A, respectively) can transport proton and alkali metal ions across a lipid membrane with ion selectivity. Fluorometric experiments using large unilamellar vesicles showed that 1 mediates proton transport across the membranes, which can be blocked by a neurotransmitter, acetylcholine, reminiscent of the blocking of the K+ channels by polyamines. The alkali metal ion transport activity of 1 follows the order of Li+ > Cs+ approximately Rb+ > K+ > Na+, which is opposite to the binding affinity of CB[6] toward alkali metal ions. On the other hand, the transport activity of 2 follows the order of Li+ > Na+, which is also opposite to the binding affinity of 2 toward these metal ions, but virtually no transport was observed for K+, Rb+, and Cs+. It is presumably because the carbonyl-fringed portal size of 2 (diameter 2.4 A) is smaller than the diameters of these alkali metal ions. To determine the transport mechanism, voltage-clamp experiments on planar bilayer lipid membranes were carried out. The experiments showed that a single-channel current of 1 for Cs+ transport is approximately 5 pA, which corresponds to an ion flux of approximately 3 x 107 ions/s. These results are consistent with an ion channel mechanism. Not only the structural resemblance to the selectivity filter of K+ channels but also the remarkable ion selectivity makes this model system unique.     

Poly(ethylene glycol) doubly and singly cationized by different alkali metal ions: Relative cation affinities and cation-dependent resolution in a quadrupole ion trap mass spectrometer

Structural information of gas phase complexes of poly(ethylene glycol) (PEG) cationized by one or two different alkali metal ions is inferred from MS and MS/MS experiments performed with an electrospray quadrupole ion trap mass spectrometer. The rationale for selecting PEG was that its sites for cation binding are non-selective with respect to the repeating monomeric unit of the polymer, but there is selectivity with respect to the formation of an inner coordination sphere specific to each metal ion. The dissociation of [M1+ M2+ (EO23)], where EO23 = linear polymer of ethylene oxide, 23 units in length, resulted in loss of one of the alkali metal ions, with preference for loss of the larger cation, with no fragmentation of the PEG backbone for Na, K, Rb, and Cs. Li was not examined in this portion of the study. The selectivity for loss of the larger alkali metal ion was [Na+ K+ (EO23)] to [Na+ (EO23)] + K+ at 100%; [K+ Rb+ (EO23)] to [K+ (EO23)] + Rb+ at 93%; and [Rb+ Cs+ (EO23)] to [Rb+ (Eo23)] + Cs+ at 99%. The resolution of [M+ (EOx)] for x = 20-30 was dependent on the alkali metal ion, with the highest resolution observed for Cs+ and the lowest for Na+. These results are discussed with respect to the packing of the oxygen atoms on PEG (M.W.(avg) = 1000) around an alkali metal ion of different radius, and how this packing leads to an ensemble of unique structures, and therefore mobilities for [M+ (EOx)].     

Extraction equilibria of various metal picrates with 19-crown-6 between benzene and water. Effect of the extra methylene group on extraction ability and selectivity

The overall extraction equilibrium constants (K(ex)) of picrates of Li(+), Na(+), K(+), Rb(+), Cs(+), Ag(+), Tl(+), and Sr(2+)with 19-crown-6 (19C6) were determined between benzene and water at 25 degrees C. The K(ex) values were analyzed into the constituent equilibrium constants, i.e. the extraction constant of picric acid, the distribution constant of the crown ether, the formation constant of the metal ion-crown ether complex in water, and the ion-pair extraction constant of the complex cation with the picrate anion. The effects of an extra methylene group of 19C6 on the extraction ability and selectivity are discussed in detail by comparing the constituent equilibrium constants of 19C6 with those of 18-crown-6 (18C6). The K(ex) value of 19C6 for each metal ion is lower than that of 18C6, which is mostly attributed to the higher lipophilicity of 19C6. The extraction ability of 19C6 for the univalent metal ions decreases in the order Tl(+)>K(+)>Rb(+)>Ag(+)>Cs(+)>Na(+)Li(+), which is the same as that observed for 18C6. The difference in logK(ex) between the univalent metals is generally smaller for 19C6 than for 18C6. The extraction selectivity of 19C6 is governed by the selectivity in the ion-pair extraction, whereas that of 18C6 depends on both the selectivities in the ion-pair extraction and in the complexation in water.     

A cation affinity series for a phosphinic acid ion-exchange resin

A cation affinity series was determined by the batch method for an ion-exchange resin with a phenylphosphinic acid group attached to a polystyrene/10% divinylbenzene matrix. The series in order of decreasing affinity is Pb(II), Mn(II), Cd(II), Ca(II), Zn(II), Mg(II), Ni(II), Ba(II), Sr(II), Co(II), Fe(III), Cs(I), Li(I), Na(I), Rb(I). These affinities are expressed quantitatively in terms of selectivity coefficients, and all ion-exchange reactions can be described in terms of simple displacement equations.     

The solvent extraction of alkali metal picrates with 4,13-N,N'-dibenzyl-4,13-diaza-18-crown-6

Extraction of alkali metal picrates with N,N'-dibenzyl-18-crown-6 was carried out, with dichloromethane as water-immiscible solvent, as a function [ligand]/[metal cation]. The extractability of metal picrates (Li(+), Na(+), K(+), Rb(+), Cs(+)) was evaluated as a function of [L]/[M(+)]. The extractability of complex cation-picrate ion pairs decreases in this sequence: Li(+)>Rb(+)>Cs(+)>K(+)>Na(+). The overall extraction equilibrium constants (K(ex)) for complexes of N,N'-dibenzyl-18-crown-6 with alkali metal picrates between dichloromethane and water have been determined at 25 degrees C. The values of the extraction constants (logK(ex)) were determined to be 10.05, 6.83, 7.12, 7.83, 6.73 for Li(+), Na(+), K(+), Rb(+) and Cs(+) compounds, respectively. DB186 shows almost 2-fold extractability against Li(+) compared to the other metal picrates, whereas it shows no obvious extractability difference amongst the other metal cations when [L]/[M(+)] is 0.2-1. However, an increasing extractability is observed for Cs(+) when [L]/[M(+)] [1].     

Study on adsorption behavior of cesium using ammonium tungstophosphate (AWP)-calcium alginate microcapsules

A functional microcapsule was prepared by encapsulating the fine crystalline ammonium tungstophosphate(AWP) in calcium alginate polymer(CaALG).The characterization of AWP-CaALG microcapsule was examined by SEM and EPMA.The adsorption behavior of Cs(I),Rb(I),Sr(II),Pd(II),Ru(III),Rh(III),La(III),Ce(III),Dy(III) and Zr(IV) was investigated by the batch method.The batch experiments were carried out by varying the shaking times,HNO 3 concentration,and initial concentration of metal ions.Relatively large K d values above 10 5 cm 3 /g for Cs(I) were obtained in the range of 0.1-5 M HNO 3,resulting in a separation factor of Cs/Rb exceeding 10 2.In contrast,the K d values of Sr(II),Pd(II),Ru(III),La(III),Dy(III),Ce(III) and Zr(IV) were considerably lower than 50 cm 3 /g.The K d value of Cs(I) decreased in the order of the coexisting ions,H + > Na + >> NH 4 +,and a linear relationship with a slop of about 1 was obtained between log K d and log [NH 4 + ]([NH 4 + ] > 0.01 M).The adsorption of Cs(I) was found to be controlled by chemisorption mechanism,and followed a Langmuir-type adsorption equation.A high uptake percentage of 99.4% for Cs(I) was obtained by using the dissolved solutions of spent fuel from FBR-JOYO(JAEA).     

Complexation of Calix[4]arene With Alkali Metal Cations: Conformational Binding Selectivity and Cation-π Driven Inclusion

Hartree-Fock, second order Møller-Plesset perturbation theory, and density functional theory calculations were carried out to analyse the complexation of calix[4]arene with cationic species including H + and the alkali metal cations (Li + , Na + , K + , Rb + , and Cs + ). Special emphasis has been placed on conformational binding selectivity, and on the structural characterization of the complexes. Li + and Na + cations are located in the calix[4]arene lower rim. The larger cations (K + , Rb + , and Cs + ) complex preferentially with the calix[4]arene cone conformer, and their endo (inclusive) complexation is driven by cation- ~ interactions, leading in the case of K + to a structure that reflects a preferential interaction with two phenol rings. The endo complexation of Cs + with calix[4]arene is in agreement with X-ray diffraction data.     

CO2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: a molecular simulation study

A molecular simulation study is reported for CO(2) adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na(+), K(+), Rb(+), Cs(+), Mg(2+), Ca(2+), and Al(3+)). The isosteric heat and Henry's constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs(+) < Rb(+) < K(+) < Na(+) < Ca(2+) < Mg(2+) < Al(3+)). At low pressures, cations act as preferential adsorption sites for CO(2) and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO(2) adsorption. Furthermore, the adsorption selectivity of CO(2)/H(2) mixture increases as Cs(+) < Rb(+) < K(+) < Na(+) < Ca(2+) < Mg(2+) ≈ Al(3+). At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H(2)O, the selectivity decreases drastically because of the competitive adsorption between H(2)O and CO(2), and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations.     

Iso-guanine quintet complexes coordinated by mono valent cations (Na+, K+, Rb+, and Cs+)

The geometric structures, the interaction energies, the vibrational characteristics, and the electronic structures of the complexes of the isoguanine (isoG) quintet coordinated with mono valent cations (Na(+), K(+), Rb(+), and Cs(+)) have been studied based on the nonplanar models. The geometry of the local minimum structure of the Na(+)-isoG quintet complex deviates significantly from the planar structure. The geometric characteristics of the Na(+)-isoG quintet complex support the experimental findings that Na(+) is unlikely to induce the formation of the isoG quintet-based pentaplexes. Similar to the guanine tetraplexes, the ionic selectivity of the isoG quintet-based pentaplexes is largely dominated by the hydration energy of the cations. After hydration correction, the positive value of the free energy difference for the formation of the Na(+)-isoG quintet complex (DeltaG(f)) suggests that the isoG quintet is unable to capture the hydrated Na(+). The negative values of DeltaG(f) for the K(+) and Rb(+) complexes implies that both ions have the tendency to be inserted into the isoG pentaplexes. This study suggests that, to elucidate the high Cs(+) selectivity of isoG pentaplexes, it is necessary to extend the model from the isoG quintet to the isoG decamer.     

Helical metallohost-guest complexes via site-selective transmetalation of homotrinuclear complexes

We have designed a new type of bis(N2O2) chelate ligand that affords a C-shaped O6 site on the metalation of the N2O2 sites. UV-vis and 1H NMR titration clearly showed that the complexation between H4L and zinc(II) acetate affords 1:3 complex [LZn3]2+ via a highly cooperative process. Although the O6-recognition site of the dinuclear metallohost [LZn2] is filled with the additional Zn2+, the O6 site can bind a guest ion with concomitant release of the initially bound Zn2+. The novel recognition process "guest exchange" took place quantitatively when rare earth metals were used as a guest. In the case of alkaline earth metals, selectivity of Ca2+ > Sr2+ > Ba2+ > Mg2+ was observed. On the other hand, the transmetalation did not take place at all when alkali metals were used for the guest. Accordingly, the trinuclear complex [LZn3]2+ is excellent in discriminating charge of the guest ions. The metallohost-guest complexes thus obtained have a helical structure, and the radius d and winding angle theta of the helix depend on the size of the guest. The La3+ complex has the smallest theta (288 degrees), and the Sc3+ complex has the largest theta (345 degrees). Because the radius and winding angles of helices are tunable by changing the guest ion, the helical metallohost-guest complexes are regarded as a molecular spring or coil. Consequently, site-specific metal exchange of trinuclear complex [LZn3]2+ described here will be utilized for highly selective ion recognition, site-selective synthesis of (3d)2(4f) trimetallic complexes, and construction of "tunable" metallohelicenes.     

Multifunctional Calix[4]arenes Containing Pendant Amide and Phosphoryl Groups: Their Use as Extracting Agents and Carriers for Alkali Cations

The complexing, extracting and mobile carrier properties of the tetra(phosphine oxide)-calix[4]arene 1 and the hybrid diamide-di(phosphine oxide)-calix[4]arene 2 were studied. Both ligands give 1 : 1 complexes with alkali cations in THF as shown by the picrate method. 1H NMR experiments were run to follow encapsulation of sodium and potassium cations. The corresponding spectra indicate C2-symmetrical structure. The observed extraction orders of the alkali picrates were as follows K+>Rb+>Li+>Cs+>Na+ for 1 and Li+>Na+>K+>Rb++ for 2. Transport kinetics was analysed by means of a model which assumes pure diffusion and which allows the evaluation of mass transfer coefficients in all systems. These coefficients and their influences on the transport rate are discussed in terms of size of the transporting species in the liquid membrane.     

Relative binding affinities of alkali metal cations to

The binding affinity and selectivity of a new ionophore, [1(8)]starand (1), toward alkali metal cations in methanol were examined through NMR titration experiments and free energy perturbation (FEP) and molecular dynamics simulations. The preference was determined to be K(+) > Rb(+) > Cs(+) > Na(+) > Li(+) in both FEP simulations and NMR experiments. The FEP simulation results were able to predict the relative binding free energies with errors less than 0.13 kcal/mol, except for the case between Li(+) and Na(+). The cation selectivity was rationalized by analyzing the radial distribution functions of the M-O and M-C distances of free metal cations in methanol and those of metal-ionophore complexes in methanol.     

Conductance Study of 1 : 1 19-Crown-6 Complexes with Various Mono- and Bivalent Metal Ions in Water

Formation constants (ML) of 1 : 1 19-crown-6 (19C6) complexes with mono- (M+) and bivalent metal ions (M2+) were determined in water at 25 °C by conductometry. The KML value of 19C6 for M+ and M2+ decreases in the order Rb+ K+ > Tl+ > Na+ = Ag+ > Li+ Cs+ and Pb2+ > Ba2+ > Sr2+ > Cd2+ > Ca2+, respectively. The selectivity for the neighboring alkali metal ions in the periodic table is lower for 19C6 than for 18-crown-6 (18C6) except for the case of Rb+ and Cs+. The same is true for the alkaline earth metal ions. Generally, the KML values of 19C6 with M2+ are greater than those with M+. For Na+ and the ions which are smaller in size than Na+ (Li+, Ca2+, Cd2+), the KML value is larger for 19C6 than for 18C6, but the contrary holds for all the other ions of larger sizes than Na+. The limiting ionic molar conductivity (°) of the 19C6–K+ complex in water at 25 °C was determined to be 43. Although 19C6 is larger than 18C6, the 19C6–K+ complex is much more mobile in water than the 18C6–K+ complex.     

Extraction equilibrium and thermodynamics of cesium with a new derivative of calix[4]biscrown

A new supermolecular recognition agent named tetra-tert-butyl-calix[4]-bis[(4-methly-1,2-phenylene-crown-6] (TertButylCalixC) was synthesized. Batchwise experiments of extraction of Na(I), K(I), Rb(I), Cs(I), Sr(II), Ba(II), Ru(III) and Fe(III) from aqueous solution with TertButylCalixC/o-nitroanisole were carried out. Effects of HNO₃ concentration, contact time and temperature on the extraction behavior were examined. The equilibrium established within 30 min implied a fast extraction kinetics. The optimal operation temperature was 298 K. Stoichiometry of TertButylCalixC and Cs(I) by electrospray ionization mass spectrometry characterization revealed 1:1 molar ratio. It was observed that the extraction system of TertButylCalixC/o-nitroanisole was effective for selective removal of Cs(I), showing remarkable separation performance.     

Modeling the selective partitioning of cations into negatively charged nanopores in water

Partitioning and transport of water and small solutes into and through nanopores are important to a variety of chemical and biological processes and applications. Here we study water structure in negatively charged model cylindrical [carbon nanotube (CNT)-like] nanopores, as well as the partitioning of positive ions of increasing size (Na+, K+, and Cs+) into the pore interior using extensive molecular dynamics simulations. Despite the simplicity of the simulation system-containing a short CNT-like nanopore in water carrying a uniformly distributed charge of qpore=-ne surrounded by n (=0,...,8) cations, making the overall system charge neutral-the results provide new and useful insights on both the pore hydration and ion partitioning. For n=0, that is, for a neutral nanopore, water molecules partition into the pore and form single-file hydrogen-bonded wire spanning the pore length. With increasing n, water molecules enter the pore from both ends with preferred orientations, resulting in a mutual repulsion between oriented water molecules at the pore center and creating a cavity-like low density region at the center. For low negative charge densities on the pore, the driving force for partitioning of positive ions into the pore is weak, and no partitioning is observed. Increasing the pore charge gradually leads to partitioning of positive ions into the pore. Interestingly, over a range of intermediate negative charge densities, nanopores display both thermodynamic as well as kinetic selectivity toward partitioning of the larger K+ and Cs+ ions into their interior over the smaller Na+ ions. Specifically, the driving force is in the order K+>Cs+>Na+, and K+ and Cs+ ions enter the pore much more rapidly than Na+ ions. At higher charge densities, the driving force for partitioning increases for all cations-it is highest for K+ ions-and becomes similar for Na+ and Cs+ ions. The variation of thermodynamic driving force and the average partitioning time with the pore charge density together suggest the presence of free energy barriers in the partitioning process. We discuss the role of ion hydration in the bulk and in the pore interior as well as of the pore hydration in determining the barrier heights for ion partitioning and the observed thermodynamic and kinetic selectivities.     

A joint experimental and theoretical study of cation-pi interactions: multiple-decker sandwich complexes of ferrocene with alkali metal ions (Li+, Na+, K+, Rb+, Cs+)

A systematic study of cation-pi interactions between alkali metal ions and the cyclopentadienyl ring of ferrocene is presented. The alkali metal (Li+, Na+, K+, Rb+, Cs+) salts of the ditopic mono(pyrazol-1-yl)borate ligand [1,1'-fc(BMe2pz)2]2- crystallize from dimethoxyethane as multiple-decker sandwich complexes with the M+ ions bound to the pi faces of the ferrocene cyclopentadienyl rings in an eta5 manner (fc = (C5H4)2Fe; pz = pyrazolyl). X-ray crystallography of the lithium complex reveals discrete trimetallic entities with each lithium ion being coordinated by only one cyclopentadienyl ring. The sodium salt forms polyanionic zigzag chains where each Na+ ion bridges the cyclopentadienyl rings of two ferrocene moieties. Linear columns [-CpR-Fe-CpR-M+-CpR-Fe-CpR-M+-](infinity) (R = [-BMe2pz]-) are established by the K+, Rb+, and Cs+ derivatives in the solid state. According to DFT calculations, the binding enthalpies of M+-eta5(ferrocene) model complexes are about 20% higher as compared to the corresponding M+-eta6(benzene) aggregates when M+ = Li+ or Na+. For K+ and Rb+, the degree of cation-pi interaction with both aromatics is about the same. The binding sequence along the M+-eta5(ferrocene) series follows a classical electrostatic trend with the smaller ions being more tightly bound.     

Characterization of Brazilian commercial milks by instrumental neutron activation analysis

Aiming at the determination of toxic and essential elements in Brazilian commercial bovine milk, 25 ultra high temperature (UHT) milk samples were acquired in the local market of Piracicaba, SP. The samples were freeze-dried and analyzed by instrumental neutron activation analysis (INAA) allowing the determination of Br, Ca, Co, Cs, Fe, K, Na, Rb and Zn. When the results were expressed as concentration (mg·l⁻¹) no significant differences were found. However, considering the dry matter, results showed a clear difference between the mass fractions (mg·kg⁻¹ d.w.) of skim milk and whole milk for the elements Br, Ca, K, Na, Rb and Zn, indicating that the removal of fat caused a concentration effect in the dry matter of skim milks. Discrepancies were found between the concentrations of Ca and Na measured by INAA and the values informed in the labels. Ca showed variations within 30% for most samples, while concentrations of Na were up to 190% higher than informed values. The sample preparation and the INAA procedure were appropriate for the determination of Br, Ca, Co, Cs, Fe, K, Na, Rb and Zn in milk samples.