The adsorption of propylene oxide,achiral molecule,o naPt(111) single-crystal surface was studied as af unction of enantiomeric composition by temperature programmed desorption (TPD) and molecular beams.T wo opposing trends were observed leading to variations in the enantiomeric excess (ee) of the chemisorbed layers with respect to the composition of the gas-phase mixtures:akinetic effect dominant during the initial uptake,w ith ap reference toward the formation of enantiopure layers,a nd as teady-state effect seen after approximately monolayer half-saturation, at which point the preference is toward racemization. These effects may account for important phenomena such as the bias toward one chirality in biological systems and the selective crystallization of some chiral compounds,a nd may also be used in practical applications for chemical separations and catalysis.When molecules contain at least one carbon atom coordinated to four different moieties,t hey can exist in two chemically identical but non-superimposable mirror-image forms.T he two so-called enantiomers,d enoted Sa nd R, are said to be chiral, aproperty that is critical in the synthesis of pharmaceuticals and other biological applications because life on earth has,for reasons not fully understood to date,chosen to operate exclusively with one type of chirality. [1,2] There is an ongoing quest to find efficient ways to produce enantiopure compounds in order to avoid complex enantiopurification steps.Efficient chiral and green chemical synthesis may be achieved by using enantioselective heterogeneous catalysts. However,t hat requires ab etter understanding of the details of the adsorption of chiral molecules on solid surfaces. [3][4][5][6][7] A number of surface-science experiments have shown that the enantiocomposition of the adsorbed layers of chiral compounds may vary relative to those in the gas or liquid phases. In particular,Y ua nd Gellman have recently shown that the enantiomeric excess (ee)o fc hiral mixtures of aspartic acid can be amplified upon adsorption on achiral Cu(111) surfaces.[8] We have also shown that the ee of surface layers of chiral compounds can be amplified by adding non-chiral adsorbates. [9] In this study,w er eport interesting variations in enantiocomposition induced by adsorption of enantio mixtures of propylene oxide (PO) on aPt(111) single-crystal surface.The coverages of the adsorbates have been determined by quantifying the yields from temperature programmed desorption (TPD) experiments,a sd one in the past by us and others. [10][11][12][13][14][15][16][17] Thet wo enantiomers of PO were differentiated by using isotope labeling,m ixing regular PO-d 0 with either PO-d 2 or PO-d 6 .T ypical data on the enantiocomposition of the adsorbates as af unction of the extent of exposure of the surface to the PO gas mixture are shown in Figure 1, in this case for a1 :1 mixture of R-PO-d 0 (denoted as R-PO in the figures) + Racemic-PO-d 6 (a 1:1m ixture of the S and R enantiomers,d enoted as Rac-PO-d 6 )a nd as urface temp...